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2022-03-29
Ab initio Approaches to High Entropy Alloys: A Comparison of CPA, SQS, and Supercell Methods
We present a comparative study of different modeling approaches to the electronic properties of the $\textrm{Hf}_{0.05}\textrm{Nb}_{0.05}\textrm{Ta}_{0.8}\textrm{Ti}_{0.05}\textrm{Zr}_{0.05}$ high entropy alloy. Common to our modeling is the methodology to compute the one-particle Green's function in the framework of density functional theory. We demonstrate that the special quasi-random structures modeling and the supercell, i.e. the locally self-consistent multiple-scatering methods provide very similar results for the ground state properties such as the spectral function (density of states) and the equilibrium lattice parameter. To reconcile the multiple-scattering single-site coherent potential approximation with the real space supercell methods, we included the effect of screening of the net charges of the alloy components. Based on the analysis of the total energy and spectral functions computed within the density functional theory, we found no signature for the long-range or local magnetic moments formation in the $\textrm{Hf}_{0.05}\textrm{Nb}_{0.05}\textrm{Ta}_{0.8}\textrm{Ti}_{0.05}\textrm{Zr}_{0.05}$ high entropy alloy, instead we find possible superconductivity below $\sim 9$K.
2203.16498v1
2016-03-24
Interplay between magnetism and energetics in FeCr alloys from a predictive non-collinear magnetic tight-binding model
Magnetism is a key driving force controlling several thermodynamic and kinetic properties of Fe-Cr systems. We present a newly-developed TB model for Fe-Cr, where magnetism is treated beyond the usual collinear approcimation. A major advantage of this model consists in a rather simple fitting procedure. In particular, no specific properties of the binary system is explicitly required in the fitting database. The present model is proved to be accurate and highly transfer-able for electronic, magnetic and energetic properties of a large variety of structural and chemical environments: surfaces, interfaces, embedded clusters, and the whole compositional range of the binary alloy. The occurence of non-collinear magnetic configurations caused by magnetic frustrations is successfully predicted. The present TB approach can apply for other binary magnetic transition-metal alloys. It is expected to be particularly promissing if the size difference between the alloying elements is rather small and the electronic properties prevail.
1603.07482v1
2017-02-16
Extended spin model in atomistic simulations of alloys
An extended atomistic spin model allowing for studies of the finite temperature magnetic properties of alloys is proposed. The model is obtained by extending the Heisenberg Hamiltonian via a parameterization from a first principles basis, interpolating from both the low temperature ferromagnetic and the high temperature paramagnetic reference states. This allows us to treat magnetic systems with varying degree of itinerant character within the model. Satisfactory agreement with both previous theoretical studies and experiments are obtained in terms of Curie temperatures and paramagnetic properties. The proposed model is not restricted to elements but is also applied to binary alloys, such as the technologically important material Permalloy, where significant differences in the finite magnetic properties of Fe and Ni magnetic moments are found. The proposed model strives to find the right compromise between accuracy and computational feasibility for accurate modeling, even for complex magnetic alloys and compounds.
1702.05011v1
2019-03-20
Effect of solute content and temperature on the deformation mechanisms and critical resolved shear stress in Mg-Al and Mg-Zn alloys
The influence of solute atoms (Al and Zn) on the deformation mechanisms and the critical resolved shear stress for basal slip in Mg alloys at 298 K and 373 K was ascertained by micropillar compression tests in combination with high-throughput processing techniques based on the diffusion couples. It was found that the presence of solute atoms enhances the size effect at 298 K as well as the localization of deformation in slip bands, which is associated with large strain bursts in the resolved shear stress ($\tau_{RSS}$)-strain ($\epsilon$) curves. Deformation in pure Mg and Mg alloys was more homogeneous at 373 K and the influence of the micropillar size on the critical resolved shear stress was much smaller. In this latter case, it was possible to determine the effect of solute content on the critical resolved shear stress for basal slip in Mg-Al and Mg-Zn alloys.
1903.08388v1
2019-03-22
Broadband Phonon Scattering in PbTe-based Materials Driven Near the Ferroelectric Phase Transition by Strain or Alloying
The major obstacle in the design of materials with low lattice thermal conductivity is the difficulty in efficiently scattering phonons across the entire frequency spectrum. Using first principles calculations, we show that driving PbTe materials to the brink of the ferroelectric phase transition could be a powerful strategy to solve this problem. We illustrate this concept by applying tensile [001] strain to PbTe and its alloys with another rock-salt IV-VI material, PbSe; and by alloying PbTe with a rhombohedral IV-VI material, GeTe. This induces extremely soft optical modes at the zone center, which increase anharmonic acoustic-optical coupling and decrease phonon lifetimes at all frequencies. We predict that PbTe, Pb(Se,Te) and (Pb,Ge)Te alloys driven close to the phase transition in the described manner will have considerably lower lattice thermal conductivity than that of PbTe (by a factor of 2-3). The proposed concept may open new opportunities for the development of more efficient thermoelectric materials.
1903.09674v1
2019-05-01
Lattice-Constant and Band-Gap Tuning in Wurtzite and Zincblende BInGaN Alloys
InGaN light-emitting diodes (LEDs) are more efficient and cost effective than incandescent and fluorescent lighting, but lattice mismatch limits the thickness of InGaN layers that can be grown on GaN without performance-degrading dislocations. In this work, we apply hybrid density functional theory calculations to investigate the thermodynamic stability, lattice parameters, and band gaps of wurtzite and zincblende quaternary BInGaN alloys. We find that the wurtzite phase is more stable and can be lattice-matched to GaN for BInGaN compositions containing up to ~30% boron. The lattice match with GaN decreases strain and enables thicker active layers that mitigate Auger recombination and increase the efficiency of the LEDs. The band gap of the alloy remains tunable throughout the visible spectrum. Our results indicate that BInGaN alloys are promising alternatives to InGaN for high-efficiency, high-power LEDs.
1905.00467v2
2019-05-09
Homogenous $In_{x}Ga_{1-x}N$ alloys on ZnO substrates: A new approach for high performance thermoelectric materials
High performance thermoelectric materials for wide-range temperature applications still remains a challenge. In this study, we have produced high-quality homogeneous $In_{0.32}Ga_{0.68}N$ on ZnO substrates, with no phase separation at high Indium content, using metal organic chemical vapor deposition for thermoelectric applications. A record high room temperature figure of merit zT is obtained of 0.86, which is five times larger than that of SiGe, the current state of the art high temperature thermoelectric material. These materials are shown to have a nearly perfect doping concentration to maximize zT regardless of the scattering mechanism. This almost one order of magnitude increase in zT is due to large electrical conductivities from oxygen co-doping as well as low thermal conductivities from alloy scattering. The maximum power factor reached was $77.98x10^{-4} W/mK^{2}$ at 300K for $In_{0.32}Ga_{0.68}N$ alloys at a carrier concentration $~6.25x10^{20} cm^{-3}$. This work indicates that $In_{x}Ga_{1-x}N$ alloys have great potential for thermoelectric applications especially at a high temperature range.
1905.03769v2
2019-05-23
Nanoporous Aluminum-Magnesium Alloy for UV enhanced spectroscopy
We report the first preparation of nanoporous Al-Mg alloy films by selective dissolution of Mg from a Mg-rich AlxMg1-x alloy. We show how to tune the stoichiometry, the porosity and the oxide contents in the final film by modulating the starting ratio between Al and Mg and the dealloying procedure. The obtained porous metal can be exploited for enhanced UV spectroscopy. In this respect, we experimentally demonstrate its efficacy in enhancing fluorescence and surface Raman scattering for excitation wavelengths of 360 nm and 257 nm respectively. Finally, we numerically show the superior performance of the nanoporous Al-Mg alloy in the UV range when compared to equivalent porous gold structures. The large area to surface ratio provided by this material make it a promising platform for a wide range of applications in UV/deep-UV plasmonics.
1905.09489v1
2019-08-28
Solid-state dewetting instability in thermally-stable nanocrystalline binary alloys
Practical applications of nanocrystalline metallic thin films are often limited by instabilities. In addition to grain growth, the thin film itself can become unstable and collapse into islands through solid-state dewetting. Selective alloying can improve nanocrystalline stability, but the impact of this approach on dewetting is not clear. In this study, two alloys that exhibit nanocrystalline thermal stability as ball milled powders are evaluated as thin films. While both alloys demonstrated dewetting behavior following annealing, the severity decreased in more dilute compositions. Ultimately, a balance may be struck between nanocrystalline stability and thin film structural stability by tuning dopant concentration.
1908.10504v2
2019-08-28
Two channel heat conduction in the superconducting state of the as-cast V$_{1-x}$Zr$_x$ alloys
We present here the temperature dependence of heat capacity ($C$($T$)) and thermal conductivity ($\kappa$($T$)) in the superconducting state as well as in the normal state of as-cast V$_{1-x}$Zr$_x$ alloys. Distinct jumps in the $C$($T$) of the alloys indicate the presence of three superconducting phases with transition temperatures $T_{C1}$ = 5.4~K, $T_{C2}$ = 8.2~K and $T_{C3}$ = 8.5~K. From the metallography micrographs, these three phases are identified to be $\beta$-V, $\gamma$-ZrV$_2$, and $\gamma'$-ZrV$_2$ respectively. Apart from these phases, $\alpha$-Zr and $\beta$-Zr phases are also detected in these samples. The experimental $\kappa$($T$) in the superconducting state of these alloys is observed to be significantly higher than that expected theoretically. Our analysis suggests that the above observation is due to the coexistence of multiple superconducting and non superconducting phases which resulted in the two-parallel channels for the conduction of heat.
1908.10570v1
2019-09-11
A Review on Superplastic Forming of Ti-6Al-4V Alloy
This paper presents a review on the superplastic forming of Ti-6Al-4V alloy, which has been used to manufacture parts of complex shapes and geometries. This paper outlines the major work carried out on this front in the past three decades. It covers various aspects related to experimental setups, including the manufacture of dies and their modifications to maintain alloy thickness uniformity after forming. A detailed study of the process parameters has also been done to note the most important physical conditions required for successful forming. This is followed by the influence of microstructure, modern applications of superplastic forming of different titanium alloys and is concluded with an insight into the future work and progress in this field.
1909.05011v2
2019-09-15
Effect of gallium doping on bubbling and helium retention in aluminum exposed to low-energy helium plasma
Surface bubbling and helium retention of pure aluminum and a solid solution of aluminum-gallium(Ga) alloy exposed to low-energy He plasma has been investigated with the fluence of 1.8E24 He/m2 at room temperature . Surface morphology observations show that after irradiation, the average size of He bubbles on Al-1.8 at.% Ga alloy is around 1.8 micro metre, smaller than that on pure Al. Ga doping noticeably increases the area density of the bubble. The thermal desorption spectroscopyshows that the release amount of He in Al-1.8 at.% Ga alloy is 1.77E21 He/m2, nearly three orders of magnitude higher than that in pure Al, whlie the He desorption peak of Al-1.8 at.% Ga alloy is 480 K, much lower than 580 K of pure Al. The results of slow positron annihilation spectroscopy (SPAS) indicate that the vacancy type defects were introduced by He plasma irradiation; and lattice distortion caused by Ga doping plays an important role in determining surface bubbling and He retention characteristics of Al-1.8 at.% Ga.
1909.06815v1
2019-12-23
Change of electronic properties on transition from high-entropy to Ni-rich (TiZrNbCu)(1-x)Ni(x) alloys
We present results of comprehensive study of electronic properties of (TiZrNbCu)(1-x)Ni(x) metallic glasses performed in broad composition range x encompassing both, high entropy (HE) range, and conventional Ni-base alloy concentration range, x >= 0.35. The electronic structure studied by photoemission spectroscopy and low temperature specific heat (LTSH) reveal a split-band structure of density of states inside valence band with d-electrons of Ti, Zr, Nb and also Ni present at Fermi level N(E_F), whereas LTSH and magnetoresistivity results show that variation of N(E_F) with x changes in Ni-base regime. The variation of superconducting transition temperatures with x closely follows that of N(E_F). The electrical resistivities of all alloys are high and decrease with increasing temperature over most of explored temperature range, and their temperature dependence seems dominated by weak localization effects over a broad temperature range (10-300 K). The preliminary study of Hall effect shows positive Hall coefficient that decreases rapidly in Ni-base alloys.
1912.11133v1
2020-02-03
New approach for FIB-preparation of atom probe specimens for aluminum alloys
Site-specific atom probe tomography (APT) from aluminum alloys has been limited by sample preparation issues. Indeed, Ga, which is conventionally used in focused-ion beam (FIB) preparations, has a high affinity for Al grain boundaries and causes their embrittlement. This leads to high concentrations of Ga at grain boundaries after specimen preparation, unreliable compositional analyses and low specimen yield. Here, to tackle this problem, we propose to use cryo-FIB for APT specimen preparation specifically from grain boundaries in a commercial Al-alloy. We demonstrate how this setup, easily implementable on conventional Ga-FIB instruments, is efficient to prevent Ga diffusion to grain boundaries. Specimens were prepared at room temperature and at cryogenic temperature (below approx. 90K) are compared, and we confirm that at room temperature, a compositional enrichment above 15 at.% of Ga is found at the grain boundary, whereas no enrichment could be detected for the cryo-prepared sample. We propose that this is due to the decrease of the diffusion rate of Ga at low temperature. The present results could have a high impact on the understanding of aluminum and Al-alloys.
2002.00992v1
2020-02-08
Multiscale modelling of precipitation hardening in Al-Cu alloys: dislocation dynamics simulations and experimental validation
The mechanisms of dislocation/precipitate interactions were analyzed in an Al-Cu alloy containing a homogeneous dispersion of $\theta'$ precipitates by means of discrete dislocation dynamics simulations. The simulations were carried out within the framework of the discrete-continuous method and the precipitates were assumed to be impenetrable by dislocations. The main parameters that determine the dislocation/precipitate interactions (elastic mismatch, stress-free transformation strains, dislocation mobility and cross-slip rate) were obtained from atomistic simulations, while the size, shape, spatial distribution and volume fraction of the precipitates were obtained from transmission electron microscopy. The predictions of the critical resolved shear stress (including the contribution of solid solution) were in agreement with the experimental results obtained by means of compression tests in micropillars of the Al-Cu alloy oriented for single slip. The simulations revealed that the most important contribution to the precipitation hardening of the alloy was provided by the stress-free transformation strains followed by the solution hardening and the Orowan mechanism due to the bow-out of the dislocations around the precipitates.
2002.03128v1
2020-02-14
Designing transformation-induced plasticity and twinning-induced plasticity Cr-Co-Ni medium entropy alloys: theory and experiment
In order to efficiently explore the nearly infinite composition space in multicomponent solid solution alloys, it is important to establish predictive design strategies and use computation-aided methods. In the present work, we demonstrated the density functional theory calculations informed design routes for realizing transformation-induced plasticity (TRIP) and twinning-induced plasticity (TWIP) in Cr-Co-Ni medium entropy alloys (MEAs). We systematically studied the effects of magnetism and chemical composition on the generalized stacking fault energy surface (gamma-surface) and showed that both chemistry and the coupled magnetic state strongly affect the gamma-surface, consequently, the primary deformation modes. Based on the calculated effective energy barriers for the competing deformation modes, we constructed composition and magnetism dependent deformation maps at both room and cryogenic temperatures. Accordingly, we proposed various design routes for achieving desired primary deformation modes in the ternary Cr-Co-Ni alloys. The deformation mechanisms predicted by our theoretical models are in nice agreement with available experimental observations in literature. Furthermore, we fabricated two non-equiatomic Cr-Co-Ni MEAs possessing the designed TWIP and TRIP effects, showing excellent combinations of tensile strength and ductility.
2002.05900v1
2020-06-01
Multifunctional behavior of Mn-site doped antiferromagnetic Mn$_5$Si$_3$ alloys
Present work reports a detailed investigation on the magnetoresistance and magnetocaloric behavior of Ni and Cr-doped Mn$_5$Si$_3$ alloys with general formula Mn$_{5-x}$A$_x$Si$_3$ (where A = Ni/Cr; $x$ = 0, 0.05, 0.1 and 0.2). Both pure (undoped) and doped alloys show a reasonably large amount of magnetoresistance (MR). Doping at Mn-site, both by Ni and Cr, results in a monotonic decrease in MR values. Magnetocaloric effect (MCE), on the other hand, is found to be interesting, and all the alloys show both conventional and inverse MCE around the magneto-structural transition temperature. Among the two types of MCE observed, the inverse MCE is found to decrease with increasing doping concentration and consistent with the MR behavior, whereas doping results in a significant increase in conventional MCE values.
2006.00865v1
2020-06-11
Low thermal conductivity of iron-silicon alloys at Earth core conditions with implications for the geodynamo
Earth core is composed of iron (Fe) alloyed with light elements, e.g., silicon (Si). Its thermal conductivity critically affects Earth thermal structure, evolution, and dynamics, as it controls the magnitude of thermal and compositional sources required to sustain a geodynamo over Earth history. Here we directly measured thermal conductivities of solid Fe and Fe-Si alloys up to 144 GPa and 3300 K. 15 at% Si alloyed in Fe substantially reduces its conductivity by about 2 folds at 132 GPa and 3000 K. An outer core with 15 at% Si would have a conductivity of about 20 W m-1 K-1, lower than pure Fe at similar pressure-temperature conditions. This suggests a lower minimum heat flow, around 3 TW, across the core-mantle boundary than previously expected, and thus less thermal energy needed to operate the geodynamo. Our results provide key constraints on inner core age that could be older than two billion-years.
2006.06271v2
2020-06-11
Relationship between grain boundary segregation and grain boundary diffusion in Cu-Ag alloys
While it is known that alloy components can segregate to grain boundaries (GBs), and that the atomic mobility in GBs greatly exceeds the atomic mobility in the lattice, little is known about the effect of GB segregation on GB diffusion. Atomistic computer simulations offer a means of gaining insights into the segregation-diffusion relationship by computing the GB diffusion coefficients of the alloy components as a function of their segregated amounts. In such simulations, thermodynamically equilibrium GB segregation is prepared by a semi-grand canonical Monte Carlo method, followed by calculation of the diffusion coefficients of all alloy components by molecular dynamics. As a demonstration, the proposed methodology is applied to a GB is the Cu-Ag system. The GB diffusivities obtained exhibit non-trivial composition dependencies that can be explained by site blocking, site competition, and the onset of GB disordering due to the premelting effect.
2006.06591v2
2020-07-30
Control of hot-carrier relaxation time in Au-Ag thin films through alloying
The plasmon resonance of a structure is primarily dictated by its optical properties and geometry, which can be modified to enable hot-carrier photodetectors with superior performance. Recently, metal-alloys have played a prominent role in tuning the resonance of plasmonic structures through chemical composition engineering. However, it has been unclear how alloying modifies the time dynamics of generated hot-carriers. In this work, we elucidate the role of chemical composition on the relaxation time of hot-carriers for the archetypal Aux Ag1-x thin-film system. Through time-resolved optical spectroscopy measurements in the visible wavelength range, we measure composition-dependent relaxation times that vary up to 8x for constant pump fluency. Surprisingly, we find that the addition of 2% of Ag into Au films can increase the hot carrier lifetime by approximately 35% under fixed fluence, as a result of a decrease in optical loss. Further, the relaxation time is found to be inversely proportional to the imaginary part of the permittivity. Our results indicate that alloying is a promising approach to effectively control hot-carrier relaxation time in metals.
2007.15561v1
2020-09-23
Indium gallium nitride quantum dots: Consequence of random alloy fluctuations for polarization entangled photon emission
We analyze the potential of the $c$-plane InGaN/GaN quantum dots for polarization entangled photon emission by means of an atomistic many-body framework. Special attention is paid to the impact of random alloy fluctuations on the excitonic fine structure and the excitonic binding energy. Our calculations show that $c$-plane InGaN/GaN quantum dots are ideal candidates for high temperature entangled photon emission as long as the underlying $C_{3v}$-symmetry is preserved. However, when assuming random alloy fluctuations in the dot, our atomistic calculations reveal that while the large excitonic binding energies are only slightly affected, the $C_{3v}$ symmetry is basically lost due to the alloy fluctuations. We find that this loss in symmetry significantly impacts the excitonic fine structure. The observed changes in fine structure and the accompanied light polarization characteristics have a detrimental effect for polarization entangled photon pair emission via the biexciton-exciton cascade. Here, we also discuss possible alternative schemes that benefit from the large excitonic binding energies, to enable non-classical light emission from $c$-plane InGaN/GaN quantum dots at elevated temperatures.
2009.11161v1
2020-09-30
Lattice Thermal Transport in Two-Dimensional Alloys and Fractal Heterostructures
Engineering thermal transport in two dimensional materials, alloys and heterostructures is critical for the design of next-generation flexible optoelectronic and energy harvesting devices. Direct experimental characterization of lattice thermal conductivity in these ultra-thin systems is challenging and the impact of dopant atoms and hetero-phase interfaces, introduced unintentionally during synthesis or as part of deliberate material design, on thermal transport properties is not understood. Here, we use non-equilibrium molecular dynamics simulations to calculate lattice thermal conductivity of (Mo|W)Se$_2$ monolayer crystals including Mo$_{1-x}$W$_x$Se$_2$ alloys with substitutional point defects, periodic MoSe$_2$|WSe$_2$ heterostructures with characteristic length scales and scale-free fractal MoSe$_2$|WSe$_2$ heterostructures. Each of these features has a distinct effect on phonon propagation in the crystal, which can be used to design fractal and periodic alloy structures with highly tunable thermal conductivities. This control over lattice thermal conductivity will enable applications ranging from thermal barriers to thermoelectrics.
2009.14508v1
2020-10-03
Interstitial Carbon in bcc HfNbTiVZr high entropy alloy from first principles
The remarkable mechanical properties of high entropy alloys can be further improved by interstitial alloying. In this work we employ density functional theory calculations to study the solution energies of dilute carbon interstitial atoms in tetrahedral and octahedral sites in bcc HfNbTiVZr. Our results indicate that carbon interstitials in tetrahedral sites are unstable, and the preferred octahedral sites present a large spread in the energy of solution. The inclusion of carbon interstitials induces large structural relaxations with long-range effects. The effect of local chemical environment on the energy of solution is investigated by performing a local cluster expansion including studies of its correlation with the carbon atomic Voronoi volume. However, the spread in solution energetics can not be explained with a local environment analysis only pointing towards a complex, long-range influence of interstitial carbon in this alloy.
2010.01354v1
2021-01-29
High temperature interaction between molten Ni50Al50 alloy and ZrB2 ultra-high temperature ceramics
In this work, Ni50Al50 alloy is taken into consideration as potential brazing material for joining ZrB2 ultra-high temperature ceramic. The results of experimental study on high temperature interfacial phenomena between molten binary Ni50Al50 alloy and polycrystalline ZrB2, are shown. A sessile drop method combined with a capillary purification procedure was applied to investigate the wetting behavior of Ni50Al50/ZrB2 couple during holding for 400 seconds at temperature of 1688{\deg}C (i.e. at T=1.02Tm). It was found that the molten Ni50Al50 rapidly wets and spreads over the surface of ZrB2, while involved reactive infiltration into the solid substrate allowed reaching a final contact angle of ~0{\deg} in 250 sec. The wetting kinetics was much faster than that reported in the literature for Cu, Ag or Au tested at T=1.05Tm. The solidified couple was subjected to SEM/EDS microstructural characterization in order to reveal a course of interfacial phenomena. The results point towards (I) an existence of Ni-enriched Ni-Al/ZrB2 surface interfacial layer; (II) a formation of infiltration zone assisted by reactively formed Al2O3 due to a reaction with Al-rich melt and (III) a partial transfer of ZrB2 phase to Ni50Al50 alloy by a dissolution/precipitation mechanism.
2101.12510v1
2021-04-16
Bandgap widening and behavior of Raman-active phonon modes of cubic single-crystalline (In,Ga)$_2$O$_3$ alloy films
The influence of Ga incorporation into cubic In$_2$O$_3$ on the electronic and vibrational properties is discussed for (In$_{1-x}$,Ga$_x$)$_2$O$_3$ alloy films grown by molecular beam epitaxy. Using spectroscopic ellipsometry, a linear dependence of the absorption onset on the Ga content $x$ is found with a blueshift of up to 150 meV for $x = 0.1$. Consistently, the fundamental band gap exhibits a blueshift as determined by hard X-ray photoelectron spectroscopy. The dependence of the absorption onset and the effective electron mass on the electron concentration is derived from the infrared dielectric functions for a Sn doped alloy film. The influence of alloying on phonon modes is analyzed on the basis of Raman spectroscopic measurements. The frequencies of several phonon modes are identified as sensitive measures for the spectroscopic determination of the Ga content.
2104.08092v2
2021-05-05
From pseudo-direct hexagonal germanium to direct silicon-germanium alloys
We present ab initio calculations of the electronic and optical properties of hexagonal SiGe alloys in the lonsdaleite structure. Lattice constants and electronic band structures in excellent agreement with experiment are obtained using density-functional theory. Hexagonal Si has an indirect band gap, while hexagonal Ge has a pseudo-direct gap, i.e. the optical transitions at the minimum direct band gap are very weak. The pseudo-direct character of pure hexagonal Ge is efficiently lifted by alloying. Already for a small admixture of Si, symmetry reduction enhances the oscillator strength of the lowest direct optical transitions. The band gap is direct for a Si content below 45 %. We validate lonsdaleite group-IV alloys to be efficient optical emitters, suitable for integrated optoelectronic applications.
2105.01980v1
2021-05-07
Atomic Origins of Friction Reduction in Metal Alloys
We present the results of large scale molecular dynamics simulations aimed at understanding the origins of high friction coefficients in pure metals, and their concomitant reduction in alloys and composites. We utilize a series of targeted simulations to demonstrate that different slip mechanisms are active in the two systems, leading to differing frictional behavior. Specifically, we show that in pure metals, sliding occurs along the crystallographic slip planes, whereas in alloys shear is accommodated by grain boundaries. In pure metals, there is significant grain growth induced by the applied shear stress and the slip planes are commensurate contacts with high friction. However, the presence of dissimilar atoms in alloys suppresses grain growth and stabilizes grain boundaries, leading to low friction via grain boundary sliding.
2105.03054v1
2021-08-08
Atomic structure, electronic structure and optical absorption of inorganic perovskite compounds Cs2SnI6-nXn (X=F, Cl, Br; n= 0~6): A first-principles study
As a possible alternative to organic-inorganic hybrid perovskite halide, inorganic Cs2SnI6 has drawn more and more research attention recently. In order to find more Cs2SnI6 derivatives as the potential solar cell absorber materials, I- ions in Cs2SnI6 are replaced by other halogen ions and forms the Cs2SnI6-nXn (X=F, Cl, Br; n=1~6) compounds, whose atomic structures, electronic structures and optical absorption are investigated by first principles calculation. When the alloying level n increases, the mean lattice constants, the weighted Sn-X and Cs-X bond lengths all decreases linearly; the bond length of each Sn-X diminishes slightly inside the octahedral structure; Eg of Cs2SnI6-nXn increases nonlinearly. Eleven Cs2SnI6-nXn compounds have an Eg between 1.0 eV and 2.0 eV and so can be potentially used as the light absorption layer of solar cells. Their partial DOS demonstrate that as the alloying level n increases, I 5p orbital in VBM and CBM is gradually substituted by Br 4p, or Cl 3p, or F 2p orbital. The eleven Cs2SnI6-nXn alloys all have a direct bandgap although the lattice distortion induced by the alloyed X- ion.
2108.03597v1
2021-08-26
An investigation of high entropy alloy conductivity using first-principles calculations
The Kubo-Greenwood equation, in combination with the first-principles Korringa-Kohn-Rostoker Coherent Potential Approximation (KKR-CPA) can be used to calculate the DC residual resistivity of random alloys at T = 0 K. We implemented this method in a multiple scattering theory based ab initio package, MuST, and applied it to the ab initio study of the residual resistivity of the high entropy alloy Al$_x$CoCrFeNi as a function of $x$. The calculated resistivities are compared with experimental data. We also predict the residual resistivity of refractory high entropy alloy MoNbTaV$_x$W. The calculated resistivity trends are also explained using theoretical arguments.
2108.11739v1
2021-09-16
Pinning of dislocations in disordered alloys: Effects of dislocation orientation
The current interest in compositionally complex alloys including so called high entropy alloys has caused renewed interest in the general problem of solute hardening. It has been suggested that this problem can be addressed by treating the alloy as an effective medium containing a random distribution of dilatation and compression centers representing the volumetric misfit of atoms of different species. The mean square stresses arising from such a random distribution can be calculated analytically, their spatial correlations are strongly anisotropic and exhibit long-range tails with third-order power law decay. Here we discuss implications of the anisotropic and long-range nature of the correlation functions for the pinning of dislocations of arbitrary orientation. While edge dislocations are found to follow the standard pinning paradigm, for dislocations of near screw orientation we demonstrate the co-existence of two types of pinning energy minima.
2109.07796v1
2021-10-04
Spatial characteristics of nickel-titanium shape memory alloy fabricated by continuous directed energy deposition
Additive manufacturing has been adopted to process nickel-titanium shape memory alloys due to its advantages of flexibility and minimal defects. The current layer-by-layer method is accompanied by a complex temperature history, which is not beneficial to the final characteristics of shape memory alloys. In this study, a continuous directed energy deposition method has been proposed to improve microstructure uniformity. The spatial characterization of nickel-titanium shape memory alloy fabricated by continuous directed energy deposition is investigated to study the temperature history, phase constituent, microstructure, and mechanical properties. The results indicate that the fabricated specimen has a monotonic temperature history, relatively uniform phase distribution and microstructure morphology, as well as high compressive strength (2982 MPa~3105 MPa) and strain (37.7%~41.1%). The reported method is expected to lay the foundation for spatial control during the printing of functional structures.
2110.01144v1
2021-10-08
Defect studies in strain-relaxed Si$_{1-x}$Ge$_x$ alloys
Raman light scattering, low-temperature photoluminescence, light-scattering tomography, and hydrogenation were used to investigate optical properties of defects in strain-relaxed Si_{1-x}Ge_x (0.05 \le x \le 0.50) alloys. The photoluminescence emission was characterized by typical zero-phonon, phonon-assisted, and dislocations-related emissions, which are dependent on Ge composition x. However, luminescence spectra exhibited above band-gap features, which are likely associated with the presence of Si-rich regions in the alloys. The results are correlated with light-scattering tomography, revealing the presence of dislocations and Si precipitates. The excess peak at 519 cm^{-1} in Ge-rich samples is supportive of this observation. At low Ge content, a dislocation-related band (D2 line) at 14,204 {\AA} dominates D-band emission for x < 0.25 while overall D-band emission intensity decreases with x. Hydrogenation was found to enhance D-band emission, indicating a passivation of nonradiative recombination centers inside dislocation cores. Si-Si, Si-Ge, and Ge-Ge phonons (TO, TA, and LA), which are participating in luminescence emission, evolve with increasing Ge content and Ge-Ge and Si-Ge TO lines dominate the Raman spectrum to the detriment of the Si-Si TO phonon line. Raman spectra reveal the presence of alloy fluctuations and possible presence of Ge particles, particularly in Ge-rich samples.
2110.04351v1
2021-10-12
Strong paramagnetic response in Y containing V$_{0.6}$Ti$_{0.4}$ superconductor
We report here, the systematic field-cooled (FC) magnetisation of superconducting (V$_{0.6}$Ti$_{0.4}$)-Y alloys in presence of applied magnetic fields upto 7 T. Paramagnetic response is clearly observed just below the superconducting transition temperature (T$_{c}$) in low fields ($\leq$0.2 T). The lower T$_{c}$ of the Y-rich precipitates as compared to the bulk, is the origin of flux compression and this leads to paramagnetic response. It is also observed that the magnetisation obtained during field cooled (FC) cooling cycle is lower than that of FC warming, for all the alloys in the field range 0.02-7 T. In addition, paramagnetic relaxation of FC moment is observed. We identify that these features of Y containing alloys are related to the high field paramagnetic Meissner effect (HFPME). Our analysis shows that the large difference in pinning strength of the different pinning centres generated due to Y addition to V$_{0.6}$Ti$_{0.4}$ alloy, is responsible for the observed effect. We provide further evidence to our claim in the form of extension of range in temperature and magnetic fields over which HFPME is observed when samples are subjected to cold work.
2110.05921v2
2021-10-27
Nanocrystalline FeCr alloys synthesised by severe plastic deformation -- a potential material for exchange bias and enhanced magnetostriction
This work gives insights into processing and characterisation of bulk nanocrystalline FeCr materials. The investigated FeCr alloys, consisting of 30, 50 and 70 at.% ferromagnetic Fe and remaining anti-ferromagnetic Cr, are processed by arc melting and subsequent severe plastic deformation by high pressure torsion. The physical similarities between elemental Fe and Cr in combination with the nanocrystalline structure of the as-deformed alloys, necessitates advanced characterisation techniques for the as-deformed state: In-situ annealing synchrotron X-ray diffraction measurements as well as electron microscopy experiments are linked to magnetostrictive measurements and reveal a single phase microstructure. Surprisingly, the nanocrystalline FeCr alloys remain supersaturated solid solutions upon annealing above 500{\deg}C, meaning a decomposition in a FeCr nanocomposite is suppressed. For the chosen annealing conditions grain growth is faster than decomposition and enhanced magnetostrictive values are found compared to materials in the as-deformed state.
2110.14303v1
2021-10-31
Edge dislocations in multi-component solid solution alloys: Beyond traditional elastic depinning
High-entropy alloys (HEA) form solid solutions with large chemical disorder and excellent mechanical properties. We investigate the origin of HEA strengthening in face-centered cubic (FCC) single-phase HEAs through molecular dynamics simulations of dislocations, in particular, the equiatomic $\rm CrCoNi$, $\rm CrMnCoNi$, $\rm CrFeCoNi$, $\rm CrMnFeCoNi$, $\rm FeNi$, and also, $\rm Fe_{0.4}Mn_{0.27}Ni_{0.26}Co_{0.05}Cr_{0.02}$, $\rm Fe_{0.7}Ni_{0.11}Cr_{0.19}$. The dislocation correlation length $\xi$, roughness amplitude $R_{a}$, and stacking fault widths $W_{SF}$ are tracked as a function of stress. All alloys are characterized by a well defined depinning stress ($\sigma_c$) and we find a novel regime where exceptional strength is observed, and a fortuitous combination takes place, of small stacking fault widths and large dislocation roughness $R_{a}$. Thus the depinning of two partials seems analogous to unconventional domain wall depinning in disordered magnetic thin films. This novel regime is identified in specific compositions commonly associated with exceptional mechanical properties ($\rm CrCoNi$, $\rm CrMnCoNi$, $\rm CrFeCoNi$, and $\rm CrMnFeCoNi$). Yield stress from analytical solute-strengthening models underestimates largely the results in these cases. A possible strategy for increasing strength in multi-component single-phase alloys is the combined design of stacking fault width and element-based chemical disorder.
2111.00568v1
2021-11-08
Biaxial Strain Modulated Valence Band Engineering in III-V Digital Alloys
Some III-V digital alloy avalanche photodiodes exhibit low excess noise. These alloys have low hole ionization coefficients due to presence of small 'minigaps', enhanced effective mass and large separation between light-hole and split-off bands in the valence band. In this letter, an explanation for the formation of the minigaps using a tight binding picture is provided. Furthermore, we demonstrate that decreasing substrate lattice constant can increase the minigap size and mass in the transport direction. This leads to reduced quantum tunneling and phonon scattering of the holes. Finally, we illustrate the band structure modification with substrate lattice constant for other III-V digital alloys.
2111.04247v1
2021-11-22
Multihyperuniform Long-Range Order in Medium-Entropy Alloys
We provide strong numerical evidence for a hidden multihyperuniform long-range order (MHLRO) in SiGeSn medium-entropy alloys (MEAs), in which the normalized infinite-wavelength composition fluctuations for all three atomic species are completely suppressed as in a perfect crystalline state. We show this MHLRO naturally leads to the emergence of short-range order (SRO) recently discovered in MEAs, which results in stable lower-energy states compared to alloy models with random or special quasi-random structures (SQSs) possessing no atomic SROs. The MHLRO MEAs approximately realize the Vegard's law, which offers a rule-of-mixture type predictions of the lattice constants and electronic band gap, and thus can be considered as an ideal mixing state. The MHLRO also directly gives rise to enhanced electronic band gaps and superior thermal transport properties at low temperatures compared to random structures and SQSs, which open up novel potential applications in optoelectronics and thermoelectrics. Our analysis of the SiGeSn system leads to the formulation of general organizing principles applicable in other medium- and high-entropy alloys (HEAs), and a highly efficient computational model for rendering realistic large-scale configurations of MEAs and HEAs.
2111.11412v1
2022-01-10
Phase Boundary Segregation in Multicomponent Alloys: A Diffuse-Interface Thermodynamic Model
Microalloying elements tend to segregate to the matrix-precipitate phase boundaries to reduce the interfacial energy. The segregation mechanism is emerging as a novel design strategy for developing precipitation-hardened alloys with significantly improved coarsening resistance for high temperature applications. In this paper, we report a nanoscopic diffuse-interface thermodynamic model that describes multicomponent segregation behavior in two-phase substitutional alloys. Following classical approaches for grain boundaries, we employ the regular solution thermodynamics to establish segregation isotherms. We show that the model recovers the Guttmann multicomponent isotherm describing local interfacial concentrations, and the generalized Gibbs adsorption isotherm that governs the total solute excess and interfacial energy. A variety of multicomponent segregation behaviors are demonstrated for a model two-phase quaternary alloy. The nature of interfacial parameters and the resulting analytic solutions make the model amenable for parameterization and comparison with atomistic calculations and experimental characterizations.
2201.03117v1
2022-01-15
The Properties of doping ZrCo
ZrCo alloy is promising to substitute uranium for handling hydrogen isotope storage in thermonuclear reactor. The alloying substitution of Zr in ZrCo with Hf or Ti can enhance the ability of anti-disproportionation. In this work, Zr$_{0.75}$Hf$_{0.25}$Co and Zr$_{0.75}$Ti$_{0.25}$Co were considered in the framework of density functional theory, aimed to investigate the properties of the alloying substitution of Zr with Hf or Ti in ZrCo. Our results found that the optimized lattice constants of the alloying substitutions, Zr$_{0.75}$Hf$_{0.25}$Co and Zr$_{0.75}$Ti$_{0.25}$Co, are smaller than ZrCo. The thermodynamic stability reduces in the order Zr$_{0.75}$Hf$_{0.25}$Co > ZrCo > Zr$_{0.75}$Ti$_{0.25}$Co, as demonstrated by the enthalpy of formation. The valence electrons are mainly localized at the ion core and the chemical bonds are polarized in Zr$_{0.75}$Hf$_{0.25}$Co and Zr$_{0.75}$Ti$_{0.25}$Co analogous to ZrCo.
2201.05805v1
2022-01-19
Visualization of Band Shifting and Interlayer Coupling in WxMo1-xS2 Alloys using Near-Field Broadband Absorption Microscopy
Beyond-diffraction-limit optical absorption spectroscopy provides profound information on the graded band structures of composition-spread and stacked two-dimensional materials, in which direct/indirect bandgap, interlayer coupling, sliding, and possible defects significantly modify their optoelectronic functionalities such as photoluminescence efficiency. We here visualize the spatially-varying band structure of monolayer and bilayer transition metal dichalcogenide alloys for the first time by using near-field broadband absorption microscopy. The near-field-spectral and -spatial diagrams manifest the excitonic band shift that results from the interplay of composition spreading and interlayer coupling. These results enable us to identify the top layer of the bilayer alloy as pure WS2. We also use the aberration-free near-field transmittance images to demarcate the exact boundaries of alloyed and pure transition metal dichalcogenides. This technology can offer new insights on various layered structures in the era of stacking science in quest of novel quantum optoelectronic devices.
2201.07732v1
2022-04-04
Efficient machine-learning model for fast assessment of elastic properties of high-entropy alloys
We combined descriptor-based analytical models for stiffness-matrix and elastic-moduli with mean-field methods to accelerate assessment of technologically useful properties of high-entropy alloys, such as strength and ductility. Model training for elastic properties uses Sure-Independence Screening (SIS) and Sparsifying Operator (SO) method yielding an optimal analytical model, constructed with meaningful atomic features to predict target properties. Computationally inexpensive analytical descriptors were trained using a database of the elastic properties determined from density functional theory for binary and ternary subsets of Nb-Mo-Ta-W-V refractory alloys. The optimal Elastic-SISSO models, extracted from an exponentially large feature space, give an extremely accurate prediction of target properties, similar to or better than other models, with some verified from existing experiments. We also show that electronegativity variance and elastic-moduli can directly predict trends in ductility and yield strength of refractory HEAs, and reveals promising alloy concentration regions.
2204.01788v1
2022-04-09
Electrical breakdown of a dielectric for the formation of a superconducting nanocontact
Electrical breakdown of the dielectric nanolayer between film electrodes of niobium and an alloy of 50% indium and 50% tin forms a bridge of this alloy between the electrodes. The bridge resistance depends on the breakdown current. The length of the bridge is equal to the thickness of the dielectric (30 nm), and its diameter is 25 nm. The calculated coherence length of the alloy at 0 K is close to the length of the bridge. The calculated critical current of a bridge with a resistance of 1 {\Omega} at a temperature of 0 K is 2 mA. It is concluded that such a bridge should have the properties of a Josephson contact at a temperature lower than the critical temperature of the alloy (6.5 K).
2204.04536v1
2022-05-04
Hole Mobility Calculation for Monolayer Molybdenum Tungsten Alloy Disulfide
A simple band model using higher order non-parabolic effect was adopted for single layer molybdenum tungsten alloy disulfide (i.e., $\mathrm{Mo}_{1-x}\mathrm{W}_x\mathrm{S}_2$). The first-principles method considering $2\times2$ supercell was used to study band structure of single layer alloy $\mathrm{Mo}_{1-x}\mathrm{W}_x\mathrm{S}_2$ and a simple band (i.e., effective mass approximation model, EMA) model with higher order non-parabolic effect was used to fit the first-principle band structures in order to calculate corresponding the hole mobility. In addition, we investigate the alloy scattering effect on the hole mobility of $\mathrm{Mo}_{1-x}\mathrm{W}_x\mathrm{S}_2$.
2205.02185v1
2022-05-23
Maximum strength and dislocation patterning in multi-principal element alloys
Multi-principal element alloys (MPEAs), commonly termed as medium- or high-entropy alloys containing three or more components in high concentrations, render a tunable chemical short-range order (SRO). Leveraging large-scale atomistic simulations, we probe the limit of Hall-Petch strengthening and deformation mechanisms in a model CrCoNi alloy and unravel chemical short-range ordering effects. It is found that, in the presence of SRO, the maximum strength is appreciably increased, and the strongest grain size drifts to a small value. Additionally, the propensity for faulting and deformation transformation is reduced and accompanied by the intensification of planar slip and strain localization. We reveal strikingly different deformation microstructures and dislocation patterns that prominently depend on crystallographic grain orientation and the number of slip planes activated during deformation. Grain of single planar slip attains the highest volume fraction of deformation-induced structure transformation, and grain with double active slip planes develops the densest dislocation network. These results advancing the fundamental understanding of deformation mechanisms and dislocation patterning in MPEAs suggest a mechanistic strategy for tuning mechanical behavior through simultaneously tailoring grain texture and local chemical order.
2205.11053v1
2022-06-04
Chemical Short-Range Ordering in a CrCoNi Medium-Entropy Alloy
The exceptional mechanical strengths of medium and high-entropy alloys have been attributed to hardening in random solid solutions. Here, we evidence non-random chemical mixings in CrCoNi alloys, resulting from short range ordering. A novel data-mining approach of electron nanodiffraction patterns enabled the study, which is assisted by neutron scattering, atom probe tomography, and diffraction simulation using first principles theory models. Results reveal two critical types of short range orders in nanoclusters that minimize the Cr and Cr nearest neighbors (L11) or segregate Cr on alternating close-packed planes (L12). The makeup of ordering-strengthened nanoclusters can be tuned by heat treatments to affect deformation mechanisms. These findings uncover a mixture of bonding preferences and their control at the nanoscopic scale in CrCoNi and provide general opportunities for an atomistic-structure study in concentrated alloys for the design of strong and ductile materials.
2206.02004v1
2022-06-15
Anomalous Ettingshausen effect in iron-carbon alloys
We have investigated the anomalous Ettingshausen effect (AEE) in iron-carbon alloys, i.e., cast irons and steel, using the lock-in thermography. All the alloys exhibit the clear AEE-induced temperature modulation, and their anomalous Ettingshausen coefficient is an order of magnitude greater than that of the pure iron at room temperature. The dimensionless figure of merit for AEE in the ductile cast iron is 55 times greater than that in the pure iron owing to the significant increase of the anomalous Ettingshausen coefficient. Our result reveals a potential of iron-carbon alloys as transverse thermoelectric materials, although the composition and microstructures optimizations are necessary.
2206.07322v2
2022-06-16
Hardness prediction of age-hardening aluminum alloy based on ensemble learning
With the rapid development of artificial intelligence, the combination of material database and machine learning has driven the progress of material informatics. Because aluminum alloy is widely used in many fields, so it is significant to predict the properties of aluminum alloy. In this thesis, the data of Al-Cu-Mg-X (X: Zn, Zr, etc.) alloy are used to input the composition, aging conditions (time and temperature) and predict its hardness. An ensemble learning solution based on automatic machine learning and an attention mechanism introduced into the secondary learner of deep neural network are proposed respectively. The experimental results show that selecting the correct secondary learner can further improve the prediction accuracy of the model. This manuscript introduces the attention mechanism to improve the secondary learner based on deep neural network, and obtains a fusion model with better performance. The R-Square of the best model is 0.9697 and the MAE is 3.4518HV.
2206.08011v1
2022-06-30
Proximity spin-orbit coupling in graphene on alloyed transition metal dichalcogenides
The negligible intrinsic spin-orbit coupling (SOC) in graphene can be enhanced by proximity effects in stacked heterostructures of graphene and transition metal dichalcogenides (TMDCs). The composition of the TMDC layer plays a key role in determining the nature and strength of the resultant SOC induced in the graphene layer. Here, we study the evolution of the proximity-induced SOC as the TMDC layer is deliberately defected. Alloyed ${\rm G/W_{\chi}Mo_{1-\chi}Se_2}$ heterostructures with diverse compositions ($\chi$) and defect distributions are simulated using density functional theory. Comparison with continuum and tight-binding models allows both local and global signatures of the metal-atom alloying to be clarified. Our findings show that, despite some dramatic perturbation of local parameters for individual defects, the low-energy spin and electronic behaviour follow a simple effective medium model which depends only on the composition ratio of the metallic species in the TMDC layer. Furthermore, we demonstrate that the topological state of such alloyed systems can be feasibly tuned by controlling this ratio.
2206.15313v1
2022-07-11
Alloying 2D VSe2 with Pt: from a charge density wave state to a disordered insulator
We have analyzed by means of scanning tunneling microscopy and spectroscopy the atomic and electronic structure of monolayers of 1T-VxPt1-xSe2 alloys grown by molecular beam epitaxy on epitaxial graphene substrates. We have focused on the composition range (0.1<x<0.35) where ferromagnetic behaviour has recently been demonstrated. For low Pt concentration, (x=0.07 and x=0.21), small domains (a few nanometres in diameter) exhibiting the characteristic superstructure of the charge density wave (CDW) state of pristine VSe2 monolayer remain visible on most of the sample surface. Thus alloying preserves the short range order of the CDW phase, although it destroys its long range order. For higher Pt concentration (x=0.35) a disordered alloy forms. It presents a fully developped gap (a few tens meV in width) at the Fermi level and is thus a disordered insulator. This gap exhibits strong variations at the nanometer scale, reflecting the local fluctuations in the composition. An unexpectedly large interaction of the TMD layer with the graphene substrate sets in for this composition range.
2207.04755v1
2022-08-02
Combinatorial Discovery of Irradiation Damage Tolerant Nano-structured W-based alloys
One of the challenges in fusion reactors is the discovery of plasma facing materials capable of withstanding extreme conditions, such as radiation damage and high heat flux. Development of fusion materials can be a daunting task since vast combinations of microstructures and compositions need to be explored, each of which requires trial-and-error based irradiation experiments and materials characterizations. Here, we utilize combinatorial experiments that allow rapid and systematic characterizations of composition-microstructure dependent irradiation damage behaviors of nanostructured tungsten alloys. The combinatorial materials library of W-Re-Ta alloys was synthesized, followed by the high-throughput experiments for probing irradiation damages to the mechanical, thermal, and structural properties of the alloys. This highly efficient technique allows rapid identification of composition ranges with excellent damage tolerance. We find that the distribution of implanted He clusters can be significantly altered by the addition of Ta and Re, which play a critical role in determining property changes upon irradiation.
2208.01271v1
2022-09-26
Accurate ab initio modeling of solid solution strengthening in high entropy alloys
High entropy alloys (HEA) represent a class of materials with promising properties, such as high strength and ductility, radiation damage tolerance, etc. At the same time, a combinatorially large variety of compositions and a complex structure render them quite hard to study using conventional methods. In this work, we present a computationally efficient methodology based on ab initio calculations within the coherent potential approximation. To make the methodology predictive, we apply an exchange-correlation correction to the equation of state and take into account thermal effects on the magnetic state and the equilibrium volume. The approach shows good agreement with available experimental data on bulk properties of solid solutions. As a particular case, the workflow is applied to a series of iron-group HEA to investigate their solid solution strengthening within a parameter-free model based on the effective medium representation of an alloy. The results reveal intricate interactions between alloy components, which we analyze by means of a simple model of local bonding. Thanks to its computational efficiency, the methodology can be used as a basis for an adaptive learning workflow for optimal design of HEA.
2209.12462v1
2022-10-12
Experimental data management platform for data-driven investigation of combinatorial alloy thin films
Experimental materials data are heterogeneous and include a variety of metadata for processing and characterization conditions, making the implementation of data-driven approaches for developing novel materials difficult. In this paper, we introduce the Thin-Film Alloy Database (TFADB), a materials data management platform, designed for combinatorially investigated thin-film alloys through various experimental tools. Using TFADB, researchers can readily upload, edit, and retrieve multidimensional experimental alloy data, such as composition, thickness, X-ray Diffraction, electrical resistivity, nanoindentation, and image data. Furthermore, composition-dependent properties from the database can easily be managed in a format adequate to be preprocessed for machine learning analyses. High flexibility of the software allows management of new types of materials data that can be potentially acquired from new combinatorial experiments.
2210.06027v1
2022-10-12
Crystallographic ordering of Al and Sn in α-Ti
Increasing attention is being paid to $\alpha$$_2$ Ti$_3$(Al,Sn) precipitation from the $\alpha$ phase of titanium alloys owing to its effect on slip band formation, localisation and the implications for fatigue performance in jet engine titanium. However, the early stages of $\alpha$$_2$ precipitation have historically been difficult to observe in TEM, neutron diffraction or atom probe analysis. Here, small angle X-ray scattering is used to reexamine the phase boundary in binary Ti-Al and Ti-Sn alloys with around 500 ppmw O. It is found that the phase boundaries in the literature are approximately correct, at 6.2 wt.% Al and 16.9 wt.% Sn, and that this favours the use of Al as a solid solution strengthener over Sn for ambient temperature applications. However, once O content and phase partitioning in $\alpha$+$\beta$ alloys are taken into account, this implies that Al$_{eq}$ limits for future alloy design of critical rotating parts should be lowered substantially.
2210.06197v2
2022-10-28
An innovative materials design protocol for the development of novel refractory high-entropy alloys for extreme environments
In the quest of new materials that can withstand severe irradiation and mechanical extremes for advanced applications (e.g. fission reactors, fusion devices, space applications, etc), design, prediction and control of advanced materials beyond current material designs become a paramount goal. Here, though a combined experimental and simulation methodology, the design of a new nanocrystalline refractory high entropy alloy (RHEA) system is established. Compositions of this alloy, assessed under extreme environments and in situ electron-microscopy, revealed both high mechanical strength and thermal stability, grain refinement under heavy ion irradiation and outstanding irradiation resistance to dual-beam irradiation and helium implantation, marked by remarkable resistance to defect generation, growth and coalescence. The experimental and modeling results, which demonstrated notable agreement, can be applied to design and rapidly assess other alloys subjected to extreme environmental conditions.
2210.16409v1
2022-11-19
A new semiconducting perovskite alloy system made possible by gas-source molecular beam epitaxy
Optoelectronic technologies are based on families of semiconductor alloys. It is rare that a new semiconductor alloy family is developed to the point where epitaxial growth is possible; since the 1950s, this has happened approximately once per decade. Here we demonstrate epitaxial thin film growth of semiconducting chalcogenide perovskite alloys in the Ba-Zr-S-Se system by gas-source molecular beam epitaxy (MBE). We stabilize the full range y = 0 ... 3 of compositions BaZrS$_{(3-y)}$Se$_y$ in the perovskite structure, up to and including BaZrSe$_3$, by growing on BaZrS$_3$ epitaxial templates. The resulting films are environmentally stable and the direct band gap ($E_g$) varies strongly with Se content, as predicted by theory, covering the range $E_g$ = 1.9 ... 1.4 eV for $y$ = 0 ... 3. This creates possibilities for visible and near-infrared (VIS-NIR) optoelectronics, solid state lighting, and solar cells using chalcogenide perovskites.
2211.10787v2
2022-12-13
Design guidelines for two-dimensional transition metal dichalcogenide alloys
Two-dimensional (2D) materials and Transition Metal Dichalcogenides (TMD) in particular are at the forefront of nanotechnology. To tailor properties for engineering applications, alloying strategies used for bulk metals in the last century need to be extended to this novel class of materials. Here we present a systematic analysis of the phase behaviour of substitutional 2D alloys in the TMD family on both the metal and chalcogenide site. The phase behaviour is quantified in terms of a metastability metric and benchmarked against systematic computational screening of configurational energy landscapes. The resulting Pettifor maps can be used to identify broad trends across chemical spaces and as starting point for setting up rational search strategies in phase space, thus allowing for targeted computational analysis of properties on likely thermodynamically stable compounds. The results presented here also constitute a useful guideline for synthesis of binary metal 2D TMDs alloys via a range of synthesis techniques.
2212.06597v1
2023-02-04
An Interpretable Boosting-based Predictive Model for Transformation Temperatures of Shape Memory Alloys
In this study, we demonstrate how the incorporation of appropriate feature engineering together with the selection of a Machine Learning (ML) algorithm that best suits the available dataset, leads to the development of a predictive model for transformation temperatures that can be applied to a wide range of shape memory alloys. We develop a gradient boosting ML surrogate model capable of predicting Martensite Start, Martensite Finish, Austenite Start, and Austenite Finish transformation temperatures with an average accuracy of more than 95% by explicitly taking care of potential distribution changes when modeling different alloy systems. We included heat treatment, rolling, extrusion processing parameters, and alloy system categorical features in the model input features to achieve more accurate and realistic results. In addition, using Shapley values, which are calculated based on the average marginal contribution of features to all possible coalitions, this study was able to gain insights into the governing features and their effect on predicted transformation temperatures, providing a unique opportunity to examine the critical parameters and features in martensite transformation temperatures.
2302.02153v1
2023-03-01
Molecular dynamics simulation of the transformation of Fe-Co alloy by machine learning force field based on atomic cluster expansion
The force field describing the calculated interaction between atoms or molecules is the key to the accuracy of many molecular dynamics (MD) simulation results. Compared with traditional or semi-empirical force fields, machine learning force fields have the advantages of faster speed and higher precision. We have employed the method of atomic cluster expansion (ACE) combined with first-principles density functional theory (DFT) calculations for machine learning, and successfully obtained the force field of the binary Fe-Co alloy. Molecular dynamics simulations of Fe-Co alloy carried out using this ACE force field predicted the correct phase transition range of Fe-Co alloy.
2303.00753v1
2023-03-16
Quasi-localized modes in crystalline high entropy alloys
High Entropy Alloys (HEAs) are designed by mixing multiple metallic species in nearly the same amount to obtain crystalline or amorphous materials with exceptional mechanical properties. Here we use molecular dynamics simulations to investigate the role of positional and compositional disorder in determining the low-frequency vibrational properties of CrMnFeCoNi HEAs. Our results show that the expected dependence of the density of states on the frequency as $D(\omega)\sim\omega^4$ is recovered for amorphous HEAs and is also observed for partially crystallized alloys with deviations that depend on the degree of crystallization. We find that the quasi-localized vibrations are still visible in crystalline HEAs, albeit suppressed compared to the corresponding amorphous alloys. Our work offers a unified perspective to describe HEA mechanical properties in terms of their vibrational density of states.
2303.09161v1
2023-04-09
Multiscale modeling of kinetic sluggishness in equiatomic NiCoCr and NiCoCrFeMn single-phase solid solutions
Complex, concentrated, multi-component alloys have been shown to display outstanding thermo-mechanical properties, that have been typically attributed to sluggish diffusion, entropic, and lattice distortion effects. Here, we investigate two metal alloys with such exemplary properties, the equiatomic, single-phase, face-centered-cubic (FCC) alloys NiCoCr and NiCoCrFeMn, and we compare their microstructural kinetics to the behaviors in a pure-Ni FCC metal. We perform long-time, kinetic Monte Carlo (kMC) simulations, and we analyze in detail the kinetics of atomic vacancies. We find that vacancies in both concentrated alloys exhibit subdiffusive thermally driven dynamics, in direct contrast to the diffusive dynamics of pure Ni. Subdiffusive dynamics shall be attributed to dynamical sluggishness, that is modeled by a fractional Brownian random walk. Furthermore, we analyze the statistics of waiting times, and we interpret long power-law-distributed rest periods as a direct consequence of barriers' energy-scales and lattice distortions.
2304.04255v1
2023-04-13
Energy landscape in NiCoCr-based middle-entropy alloys
NiCoCr middle-entropy alloy is known for its exceptional strength at both low and elevated operating temperatures. Mechanical properties of NiCoCr-based alloys are affected by certain features of the energy landscape, such as the energy difference between the hcp and fcc phases (which is known to correlate with the stacking fault energy in the fcc phase) and curvature of the energy surface. We compute formation energies in the Ni-Co-Cr ternary and related quaternary systems and investigate dependences of the relative energies on composition. Such computed composition-structure-property relations can be useful for tuning composition and designing next-generation alloys with improved strength.
2304.06852v1
2023-08-04
Ambient Temperature Growth and Superconducting Properties of Ti-V Alloy Thin Films
A study on the optimization of ambient temperature growth and superconducting properties of Ti-V alloy thin films grown on SiO2-coated Si substrate is reported here. These films have been synthesized by co-sputtering of Ti and V targets, and films having different Ti concentrations were deposited to get the optimized critical temperature (TC) of thin films close to the bulk value. The maximum TC of 5.2 K has been obtained in the Ti40V60 composition, which is further increased to 6.2 K when a 10 nm thick Ti underlayer is added below the Ti-V film. GIXRD measurements confirm the formation of Ti-V alloys in the desired crystal structure. The upper critical field (HC2) of the thin films has been estimated with the help of magnetotransport measurements. The utility of Ti-V alloy thin films in superconducting radiation detection applications is ascertained.
2308.02303v1
2023-08-26
Effect of Composition on Microstructural Evolution during Homogenization of 7XXX Alloys
The effect of composition on microstructure both at the length scale of the secondary dendrite arm spacing and nano-sized dispersoids during homogenization of Al-Zn-Cu-Mg-Zr alloys has been studied. A comprehensive model that can predict the microstructure at both the length scales has been used for the study. The microstructure predicted has been compared to that for two homogenized samples from a directionally solidified AA7050 sample and a reasonable match has been found. The initial as-cast microstructure for different compositions is calculated using Scheil type solidification from Thermo-Calc. The initial microstructure has a considerable influence on microstructural evolution during homogenization. To take advantage of the decreased solid solubility of Zr in {\alpha}-fcc, cooling rates during solidification must be high enough to prevent precipitation of primary Al3Zr. Under solidification with industrial cooling conditions solute rich alloys leads to fewer dispersoids. Based on the study, an improved composition range of 6-8%Zn, 1-2%Cu, 1-2%Mg and 0.1-0.15%Zr for 7XXX alloys has been proposed.
2308.13799v1
2023-09-18
Superconductivity in the bcc-type High-entropy Alloy TiHfNbTaMo
X-ray powder diffraction, electrical resistivity, magnetization, and thermodynamic measurements were conducted to investigate the structure and superconducting properties of TiHfNbTaMo, a novel high-entropy alloy possessing a valence electron count (VEC) of 4.8. The TiHfNbTaMo HEA was discovered to have a body-centered cubic structure and a microscopically homogeneous distribution of the constituent elements. This material shows type-II superconductivity with Tc = 3.42 K, lower critical field with 22.8 mT, and upper critical field with 3.95 T. Low-temperature specific heat measurements show that the alloy is a conventional s-wave type with a moderately coupled superconductor. First-principles calculations show that the density of states (DOS) of the TiHfNbTaMo alloy is dominated by hybrid d orbitals of these five metal elements. Additionally, the TiHfNbTaMo HEA exhibits three van Hove singularities. Furthermore, the VEC and the composition of the elements (especially the Nb elemental content) affect the Tc of the bcc-type HEA.
2309.09494v1
2023-09-19
First-principles characterization of thermal conductivity in LaPO4-based alloys
Alloys based on lanthanum phosphate (LaPO$_{4}$) are often employed as thermal barrier coatings, due to their low thermal conductivity and structural stability over a wide temperature range. To enhance the thermal-insulation performance of these alloys, it is essential to comprehensively understand the fundamental physics governing their heat conduction. Here, we employ the Wigner formulation of thermal transport in conjunction with first-principles calculations to elucidate how the interplay between anharmonicity and compositional disorder determines the thermal properties of La$_x$Gd$_{1{-}x}$PO$_{4}$ alloys, and discuss the fundamental physics underlying the emergence and coexistence of particle-like and wave-like heat-transport mechanisms. Our predictions for microscopic vibrational properties (temperature-dependent Raman spectrum) and for macroscopic thermal conductivity are validated against experiments. Finally, we leverage these findings to devise strategies to optimize the performance of thermal barrier coatings.
2309.10789v1
2023-09-21
Composition-based phase stability model for multicomponent metal alloys
The vastness of the space of possible multicomponent metal alloys is hoped to provide improved structural materials but also challenges traditional, low-throughput materials design efforts. Computational screening could narrow this search space if models for materials stability and desired properties exist that are sufficiently inexpensive and accurate to efficiently guide experiments. Towards this effort, here we develop a method to rapidly assess the thermodynamic stability of a metal alloy composition of arbitrary number of elements, stoichiometry, and temperature based on density functional theory (DFT) data. In our model, the Gibbs free energy of the solid solution contains binary enthalpy contributions and ideal configurational entropy, whereas only enthalpy is considered for intermetallic competing phases. Compared to a past model for predicting the formation of single-phase high-entropy alloys [Phys. Rev. X 5, 011041 (2015)], our method is similarly inexpensive, since it assesses enthalpies based on existing DFT data, but less heuristic, more broadly applicable, and more accurate (70--75%) compared to experiment.
2309.12222v1
2023-10-11
Surface segregation in high-entropy alloys from alchemical machine learning
High-entropy alloys (HEAs), containing several metallic elements in near-equimolar proportions, have long been of interest for their unique mechanical properties. More recently, they have emerged as a promising platform for the development of novel heterogeneous catalysts, because of the large design space, and the synergistic effects between their components. In this work we use a machine-learning potential that can model simultaneously up to 25 transition metals to study the tendency of different elements to segregate at the surface of a HEA. We use as a starting point a potential that was previously developed using exclusively crystalline bulk phases, and show that, thanks to the physically-inspired functional form of the model, adding a much smaller number of defective configurations makes it capable of describing surface phenomena. We then present several computational studies of surface segregation, including both a simulation of a 25-element alloy, that provides a rough estimate of the relative surface propensity of the various elements, and targeted studies of CoCrFeMnNi and IrFeCoNiCu, which provide further validation of the model, and insights to guide the modeling and design of alloys for heterogeneous catalysis.
2310.07604v2
2023-10-11
Revolutionising inverse design of magnesium alloys through generative adversarial networks
The utility of machine learning (ML) techniques in materials science has accelerated materials design and discovery. However, the accuracy of ML models - particularly deep neural networks - heavily relies on the quality and quantity of the training data. Data collection methods often have limitations arising from cost, difficulty, and resource-intensive human efforts. Thus, limited high-quality data, especially for novel materials, poses a significant challenge in developing reliable ML models. Generative adversarial networks (GANs) offer one solution to augment datasets through synthetic sample generation. The present work explores the application of GANs in magnesium (Mg) alloy design, by training two deep neural networks within the structure of a Wasserstein GAN to generate new (novel) alloys with desired mechanical properties. This data augmentation-based strategy contributes to model robustness, particularly in cases where traditional data collection is impractical. The approach presented may expedite Mg alloy development, through a GAN assisted inverse design approach.
2310.07836v3
2023-10-26
Local Coordination Modulates the Reflectivity of Liquefied Si-Ge Alloys
The properties of liquid Si-Ge binary systems at melting conditions deviate from those expected by the ideal alloy approximation. Particularly, a non-linear dependence of the dielectric functions occurs with the reflectivity of liquid Si-Ge reaching a maximum at 50\% Ge content, being 10\% higher than in pure Si or Ge. Using \textit{ab initio} methodologies, we modelled liquefied Si-Ge alloys, unveiling very high coordination numbers and poor symmetry in the first coordination shell with respect to Si and Ge, related to different bonding properties. We simulated optical functions, quantitatively replicating the aforementioned reflectivity trend and we highlighted a direct relationship between atomic structure and optical properties, indicating that the unusual optics arises from Si-Ge higher local coordination characterized by low symmetry. We forecast further implications for the overall class of these alloys. These findings expand our comprehension of liquefied semiconductors and are essential for implementing controlled laser melting procedures to highly dope these materials for advanced transistors, superconductors, sensors and plasmonic devices.
2310.17205v2
2023-10-27
CELL: a Python package for cluster expansion with a focus on complex alloys
We present the Python package CELL, which provides a modular approach to the cluster expansion (CE) method. CELL can treat a wide variety of substitutional systems, including one-, two-, and three-dimensional alloys, in a general multi-component and multi-sublattice framework. It is capable of dealing with complex materials comprising several atoms in their parent lattice. CELL uses state-of-the-art techniques for the construction of training data sets, model selection, and finite-temperature simulations. The user interface consists of well-documented Python classes and modules (http://sol.physik.hu-berlin.de/cell/). CELL also provides visualization utilities and can be interfaced with virtually any ab initio package, total-energy codes based on interatomic potentials, and more. The usage and capabilities of CELL are illustrated by a number of examples, comprising a Cu-Pt surface alloy with oxygen adsorption, featuring two coupled binary sublattices, and the thermodynamic analysis of its order-disorder transition; the demixing transition and lattice-constant bowing of the Si-Ge alloy; and an iterative CE approach for a complex clathrate compound with a parent lattice consisting of 54 atoms.
2310.18223v1
2023-11-04
Effect of W alloying on the electronic structure, phase stability and thermoelectric properties of epitaxial CrN films
The effects of W alloying on the electronic structure, phase stability, and thermoelectric properties of Cr1-xWxN films with 0 \leq x \leq 0.48 are reported. Ab initio calculations indicate that dilute W alloying (x = 0.03) results in flat bands from W 5d states and pushes the Fermi level EF into the conduction band, while retaining dispersive Cr 3d bands. These features are collectively conducive for both high electrical conductivity \sigma and high Seebeck coefficient \alpha. Epitaxial Cr1-xWxN films grown on c-plane sapphire by dc-magnetron sputtering show that \sigma increases with W additions of x \leq 0.2. Higher W levels results in the formation of metallic Cr2N and W precipitation, yielding high \sigma but low \alpha. These findings suggest that restricting the W level to below its solubility limit in CrN is key to realizing high thermoelectric properties in Cr1-xWxN alloys.
2311.02453v1
2023-11-13
The High-dimensional Phase Diagram and the Large CALPHAD Model
When alloy systems comprise more than three elements, the visualization of the entire phase space becomes not only daunting but is also accompanied by a data surge. Addressing this complexity, we delve into the FeNiCrMn alloy system and introduce the Large CALPHAD Model (LCM). The LCM acts as a computational conduit, capturing the entire phase space. Subsequently, this enormous data is systematically structured using a high-dimensional phase diagram, aided by hash tables and Depth-first Search (DFS), rendering it both digestible and programmatically accessible. Remarkably, the LCM boasts a 97% classification accuracy and a mean square error of 4.80*10-5 in phase volume prediction. Our methodology successfully delineates 51 unique phase spaces in the FeNiCrMn system, exemplifying its efficacy with the design of all 439 eutectic alloys. This pioneering methodology signifies a monumental shift in alloy design techniques or even multi-variable problems.
2311.07174v1
2023-12-11
Uncovering high-dimensional phase space and the application of Mixture of Experts (MoE) on building the Large CALPHAD Model (LCM)
This study presents a novel approach for analyzing and establishing Large CALPHAD model (LCM) in complex alloy systems. Through the introduction of "composition space volume", a multi-dimensional metric which allows to quatitatively define alloy composition variations. Utilizing stochastic methods, the study quantifies phase space complexity through phase density, and model training costs through data density. This leads to a strategic segmentation of the entire composition space, tailored to the complexity of each segment, thereby reducing computational efforts in model training. A significant advancement is the integration of segmented models using a Mixture of Experts (MoE) approach, ensuring accurate portrayal of phase behaviors across diverse composition spaces. This technique is demonstrated in establishing a high-dimensional phase diagram for the FeCoNiTi system, highlighting its efficiency and accuracy. The study's methodologies offer a systematic and cost-effective framework for modeling complex alloy systems, marking a step forward in the field of alloy design and analysis.
2312.06429v1
2023-12-26
Compositional Search of Stable Crystalline Structures in Multi-Component Alloys Using Generative Diffusion Models
Exploring the vast composition space of multi-component alloys presents a challenging task for both \textit{ab initio} (first principles) and experimental methods due to the time-consuming procedures involved. This ultimately impedes the discovery of novel, stable materials that may display exceptional properties. Here, the Crystal Diffusion Variational Autoencoder (CDVAE) model is adapted to characterize the stable compositions of a well studied multi-component alloy, NiFeCr, with two distinct crystalline phases known to be stable across its compositional space. To this end, novel extensions to CDVAE were proposed, enhancing the model's ability to reconstruct configurations from their latent space within the test set by approximately 30\% . A fact that increases a model's probability of discovering new materials when dealing with various crystalline structures. Afterwards, the new model is applied for materials generation, demonstrating excellent agreement in identifying stable configurations within the ternary phase space when compared to first principles data. Finally, a computationally efficient framework for inverse design is proposed, employing Molecular Dynamics (MD) simulations of multi-component alloys with reliable interatomic potentials, enabling the optimization of materials property across the phase space.
2312.16073v1
2024-01-12
Capturing short-range order in high-entropy alloys with machine learning potentials
Chemical short-range order (SRO) affects the distribution of elements throughout the solid-solution phase of metallic alloys, thereby modifying the background against which microstructural evolution occurs. Investigating such chemistry-microstructure relationships requires atomistic models that act at the appropriate length scales while capturing the intricacies of chemical bonds leading to SRO. Here we consider various approaches for the construction of training data sets for machine learning potentials (MLPs) for CrCoNi and evaluate their performance in capturing SRO and its effects on materials quantities of relevance for mechanical properties, such as stacking-fault energy and phase stability. It is demonstrated that energy accuracy on test sets often does not correlate with accuracy in capturing material properties, which is fundamental in enabling large-scale atomistic simulations of metallic alloys with high physical fidelity. Based on this analysis we systematically derive design principles for the rational construction of MLPs that capture SRO in the crystal and liquid phases of alloys.
2401.06622v1
2024-01-15
Fatigue Behavior of High-Entropy Alloys
High-entropy alloys (HEAs) refer to alloys composed of five or more elements in equal or near-equal amounts or in an atomic concentration range of 5 to 35 atomic percent (at%). Different elemental ratios will affect the microstructures of HEAs and provide them with unique properties. Based on past research, HEAs have exhibited superior performance, relative to most conventional alloys, with respect to many properties, such as strength, toughness, corrosion resistance, magnetic behavior, etc. Among them, fatigue behavior has been a topic of focus, due to its importance in industrial applications. In this article, we summarized the research progress in the HEA-fatigue behavior in the past ten years, including experimental results and theoretical studies in subdivisions, such as high-cycle fatigue, low-cycle fatigue, fatigue-crack growth, fatigue mechanisms, etc. The influence of the processing and test methods on HEAs is described. The accuracy of several commonly used prediction models is also outlined. Finally, unresolved issues and suggestions on the direction of future research efforts are presented.
2401.07418v1
2024-02-07
Hot Carriers from Intra- and Interband Transitions in Gold-Silver Alloy Nanoparticles
Hot electrons and holes generated from the decay of localized surface plasmons in metallic nanoparticles can be harnessed for applications in solar energy conversion and sensing. In this paper, we study the generation of hot carriers in large spherical gold-silver alloy nanoparticles using a recently developed atomistic modelling approach that combines a solution of Maxwell's equations with large-scale tight-binding simulations. We find that hot-carrier properties depend sensitively on the alloy composition. Specifically, nanoparticles with a large gold fraction produce hot carriers under visible light illumination while nanoparticles with a large silver fraction require higher photon energies to produce hot carriers. Moreover, most hot carriers in nanoparticles with a large gold fraction originate from interband transitions which give rise to energetic holes and "cold" electrons near the Fermi level. Increasing the silver fraction enhances the generation rate of hot carriers from intraband transitions which produce energetic electrons and "cold" holes. These findings demonstrate that alloy composition is a powerful tuning parameter for the design of nanoparticles for applications in solar energy conversion and sensing that require precise control of hot-carrier properties.
2402.05292v1
2024-02-26
The influence of the phase and structural state on the low-temperature elastic properties of molybdenum-alloyed non-equiatomic high-entropy alloys of the Fe-Co-Ni-Cr system
The mechanical properties and microstructural evolution of a medium-entropy alloy Co$_{17.5}$Cr$_{12.5}$Fe$_{55}$Ni$_{10}$Mo$_{5}$ (at%) in a low temperature range (including the record low temperatures region down to 0.5 K) were investigated. It has been established that low-temperature plastic deformation initiates martensitic phase transformations in this alloy, and the values of the dynamic modulus of elasticity correlate with the degree of phase transformations.
2402.17064v2
2024-02-29
Mixed-halide perovskite alloys $\text{CsPb}(\text{I}_{1-x}^{}\text{Br}_x^{})_3^{}$ and $\text{CsPb}(\text{Br}_{1-x}^{}\text{Cl}_x^{})_3^{}$: New insight of configuration entropy effect from first principles and phase diagrams
Stability is one of the key issues in mixed-halide perovskite alloys which are promising in emergent optoelectronics. Previous density-functional-theory (DFT) and machine learning studies indicate that the formation-energy convex hulls of these materials are very shallow, and stable alloy compositions are rare. In this work, we revisit this problem using DFT with special focus on the effects of configuration and vibration entropies. Allowed by the $20$-atomic models for the $\text{CsPb}(\text{I}_{1-x}^{}\text{Br}_x^{})_3^{}$ and $\text{CsPb}(\text{Br}_{1-x}^{}\text{Cl}_x^{})_3^{}$ series, the partition functions and therewith thermodynamic state functions are calculated by traversing all possible mixed-halide configurations. We can thus evaluate the temperature- and system-dependent configuration entropy, which largely corrects the conventional approach based on the ideal solution model. Finally, temperature-composition phase diagrams that include $\alpha$, $\beta$, $\gamma$ and $\delta$ phases of both alloys are constructed based on the free energy data, for which the contribution of phonon vibrations is included.
2402.19274v1
2024-03-14
A Processing Route to Chalcogenide Perovskites Alloys with Tunable Band Gap via Anion Exchange
We demonstrate synthesis of BaZr(S,Se)3 chalcogenide perovskite alloys by selenization of BaZrS3 thin films. The anion-exchange process produces films with tunable composition and band gap without changing the orthorhombic perovskite crystal structure or the film microstructure. The direct band gap is tunable between 1.5 and 1.9 eV. The alloy films made in this way feature 100x stronger photoconductive response and a lower density of extended defects, compared to alloy films made by direct growth. The perovskite structure is stable in high-selenium-content thin films with and without epitaxy. The manufacturing-compatible process of selenization in H2Se gas may spur the development of chalcogenide perovskite solar cell technology.
2403.09016v1
2024-04-11
Point defects in CdTe and CdTeSe alloy: a first principles investigation with DFT+U
CdTe and its alloy CdTeSe are widely used in optoelectronic devices, such as radiation detectors and solar cells, due to their superior electrical properties. However, the formation of defects and defect complexes in these materials can significantly affect their performance. As a result, understanding the defect formation and recombination processes in CdTe and CdTeSe alloy is of great importance. In recent years, density functional theory (DFT) calculations have emerged as a powerful tool for investigating the properties of defects in semiconductors. In this paper, we use DFT+U calculations to comprehensively study the properties of intrinsic defects as well as extrinsic defects induced by commonly used dopants, such as Cu and group V elements, in CdTe and CdTeSe alloy. This work provides insights into the effects of these defects on the electrical and optical properties of the material.
2404.07796v1
2013-07-29
Effect of surface hydrogen on the anomalous surface segregation behavior of Cr in Fe-rich Fe-Cr alloys
The segregation behavior of Cr in dilute Fe-Cr alloys is known to be anomalous since the main barrier for surface segregation of Cr in these alloys arises not from the topmost surface layer but from the subsurface layer where the solution energy of Cr is much more endothermic as compared to the topmost surface layer. The Fe-Cr alloys are candidate structural materials for the new generation of nuclear reactors. The surfaces of these alloys will be exposed to hydrogen or its isotopes in these reactors, and although hydrogen is soluble neither in Fe nor in Fe-Cr alloys, it is known that the adsorption energy of hydrogen on the surface of iron is not only exothermic but relatively large. This clearly raises the question of the effect of the hydrogen adsorbed on the surface of iron on the segregation behavior of chromium towards the surface of iron. In this paper we show, on the basis of our ab initio density functional theory calculations, that the presence of hydrogen on the surface of iron leads to a considerably reduced barrier for Cr segregation to both the topmost surface layer and the subsurface layer, but the subsurface layer still controls the barrier for surface segregation. This reduction in the barrier for surface segregation is due to the nature of the Cr-H couple that acts in a complex and synergistic manner. The presence of Cr enhances the exothermic nature of hydrogen adsorption that in turn leads to a reduced barrier for surface segregation. These results should be included in the multiscale modeling of Fe-Cr alloys.
1307.7588v1
2017-01-11
Using transmission Kikuchi diffraction to characterise α variants in an α + β titanium alloy
Two phase titanium alloys are important for high performance engineering components, such as aeroengine discs. The microstructures of these alloys are tailored during thermomechanical processing to precisely control phase factions, morphology and crystallographic orientations. In bimodal two phase ({\alpha} + {\beta}) Ti-6Al-2Sn-4Zr-2Mo (Ti-6242) alloys there are often three microstructural lengthscales to consider: large (~10 {\mu}m) equiaxed primary {\alpha}; >200 nm thick plate {\alpha} with a basketweave morphology; and very fine scaled (>50 nm plate thickness) secondary {\alpha} that grows between the larger {\alpha} plates surrounded by retained {\beta}. In this work, we utilise high spatial resolution transmission Kikuchi diffraction (TKD, also known as transmission based electron backscatter diffraction, t-EBSD) and scanning electron microscopy (SEM) based forward scattering electron imaging to resolve the structures and orientations of basketweave and secondary {\alpha} in Ti-6242. We analyse the {\alpha} variants formed within one prior {\beta} grain, and test whether existing theories of habit planes of the phase transformation are upheld. Our analysis is important in understanding both the thermomechanical processing strategy of new bimodal two-phase titanium alloys, as well the ultimate performance of these alloys in complex loading regimes such as dwell fatigue. Our paper champions the significant increase in spatial resolution afforded using transmission techniques, combined with the ease of SEM based analysis using conventional electron backscatter diffraction (EBSD) systems and forescatter detector (FSD) imaging, to study the nanostructure of real-world engineering alloys.
1701.03014v2
2017-03-31
Evolution of Raman spectra in Mo$_{1-x}$W$_x$Te$_2$ alloys
The structural polymorphism in transition metal dichalcogenides (TMDs) provides exciting opportunities for developing advanced electronics. For example, MoTe$_2$ crystallizes in the 2H semiconducting phase at ambient temperature and pressure, but transitions into the 1T$^\prime$ semimetallic phase at high temperatures. Alloying MoTe$_2$ with WTe$_2$ reduces the energy barrier between these two phases, while also allowing access to the T$_d$ Weyl semimetal phase. The MoWTe$_2$ alloy system is therefore promising for developing phase change memory technology. However, achieving this goal necessitates a detailed understanding of the phase composition in the MoTe$_2$-WTe$_2$ system. We combine polarization-resolved Raman spectroscopy with X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) to study MoWTe$_2$ alloys over the full compositional range x from 0 to 1. We identify Raman and XRD signatures characteristic of the 2H, 1T$^\prime$, and T$_d$ structural phases that agree with density-functional theory (DFT) calculations, and use them to identify phase fields in the MoTe$_2$-WTe$_2$ system, including single-phase 2H, 1T$^\prime$, and T$_d$ regions, as well as a two-phase 1T$^\prime$ + T$_d$ region. Disorder arising from compositional fluctuations in MoWTe$_2$ alloys breaks inversion and translational symmetry, leading to the activation of an infrared 1T$^\prime$-MoTe$_2$ mode and the enhancement of a double-resonance Raman process in 2H-MoWTe$_2$ alloys. Compositional fluctuations limit the phonon correlation length, which we estimate by fitting the observed asymmetric Raman lineshapes with a phonon confinement model. These observations reveal the important role of disorder in MoWTe$_2$ alloys, clarify the structural phase boundaries, and provide a foundation for future explorations of phase transitions and electronic phenomena in this system.
1703.10985v1
2018-11-21
Beneficial influence of Hf and Zr additions to Nb4at.%Ta on the vortex pinning of Nb$_{3}$Sn with and without an O source
Here we show that addition of Hf to Nb4Ta can significantly improve the high field performance of Nb$_{3}$Sn, making it suitable for dipole magnets for Future Circular Collider (FCC). A big challenge for the FCC is that a realistic production target for FCC Nb3Sn requires ~30% improvement over current conductor performance. Recent success with internal oxidation(IO) of Nb-Zr precursor has shown significant improvement in the layer J$_{c}$ of Nb$_{3}$Sn wires, albeit the complication of providing an internal O$_{2}$ diffusion path and avoiding degradation of irreversibility field($_{irr}$). We compare Zr and Hf additions to the standard Nb4Ta alloy of maximum H$_{c2}$ and H$_{irr}$. Nb4Ta rods with 1Zr or 1Hf were made into monofilament wires with and without SnO$_{2}$ and their properties measured over the entire superconducting range up to 31 T. We found that group IV alloying of Nb4Ta raises H$_{irr}$, though adding O$_{2}$ still degrades this slightly. As noted in Nb1Zr studies, the pinning force density F$_{p}$ is strongly enhanced and its peak value shifted to higher field by IO. A surprising result of this work is that we found better properties in Nb4Ta1Hf without SnO$_{2}$, F$_{pmax}$ achieving 2.35 times that of the standard Nb4Ta alloy, while the oxidized Nb4Ta1Zr alloy achieved 1.54 times that of the Nb4Ta alloy. The highest layer J$_{c}$ (16 T, 4.2 K) of 3700 A/mm$^{2}$ was found in the SnO$_{2}$-free wire made with Nb4Ta1Hf alloy. Using a standard A15 cross-section fraction of 60% for modern PIT and RRP wires, we estimated that a non-Cu J$_{c}$ of 2200 A/mm$^{2}$ is obtainable in modern conductors, well above the 1500A/mm$^{2}$ FCC specification. Moreover, the best properties were obtained without SnO$_{2}$, the Nb4Ta1Hf alloy appears to open a straightforward route to enhanced properties in Nb$_{3}$Sn wires.
1811.08867v1
2022-03-06
Hall coefficient in amorphous alloys: critical behavior and quantitative test of quantum corrections due to weak localization and electron-electron interactions
Here, we present the measurements of $R_H$ in a series of $Ti_xSi_{100-x}$ amorphous reaching the critical concentration, $x_c\approx9-9.5$. For $x\geq17$, the Hall coefficient displays the behavior predicted by the perturbation theory, $R_H^{-1}\left(T\right)=R_H^{-1}\left(0\right)+bT^{1/2}$, which extends up to the temperature 150 K. The temperature dependence gets stronger in alloys with lower $x$; $R_H\left(0\right)$ diverges at $x_c$ displaying critical behavior. We used the combined conductivity and Hall coefficient data for alloys with high Ti content to test the theories of quantum corrections to conductivity. We found that the correction due to weak localization is dominated by the electron-phonon scattering with the rate varying with temperature as $\tau_{ep}^{-1}=A_{ep}T^2$. The extracted parameter $A_{ep}$ is in good agreement with the theory that considers the incomplete drag of impurities by lattice vibrations. The spin-orbit scattering time extracted from the weak localization correction was found to be two orders of magnitude larger than the time given by the standard estimate $\tau_{so}\approx\tau\left(\hbar c/e^2Z\right)^4$. The theory of the EEI quantum correction was tested using the Hall coefficient and specific heat data for Ti-Si and $\left(Ag_{0.5}Cu_{0.5}\right)_{100-x}Ge_x$ amorphous alloys, which allowed us to estimate all microscopic parameters needed by the theory. We found that, within the accuracy of our measurements, the EEI theory works exactly for alloys that follow the free electron model [$\left(Ag_{0.5}Cu_{0.5}\right)_{100-x}Ge_x$ with $x\le50$.] The deviation from the theory observed in all Ti-Si alloys and in Ag-Cu-Ge alloys with $x\geq60$ can be qualitatively explained by weakening of the electron screening in the systems.
2203.03029v1
2021-09-01
Electronic and optical properties of Si$_{x}$Ge$_{1-x-y}$Sn$_{y}$ alloys lattice-matched to Ge
We present a combined experimental and theoretical analysis of the evolution of the near-band gap electronic and optical properties of Si$_{x}$Ge$_{1-x-y}$Sn$_{y}$ alloys lattice-matched to Ge and GaAs substrates. We perform photoreflectance (PR) and photoluminescence (PL) measurements on Si$_{x}$Ge$_{1-x-y}$Sn$_{y}$ epitaxial layers grown via chemical vapour deposition, for Si (Sn) compositions up to $x =$ 9.6% ($y =$ 2.5%). Our measurements indicate the presence of an indirect fundamental band gap, with PL observed $\approx$ 200-250 meV lower in energy than the direct $E_0$ transition identified by PR measurements. The measured PL is Ge-like, suggesting that the alloy conduction band (CB) edge is primarily derived from the Ge L-point CB minimum. Interpretation of the PR and PL measurements is supported by atomistic electronic structure calculations. Effective alloy band structures calculated via density functional theory confirm the presence of an indirect fundamental band gap, and reveal the origin of the observed inhomogeneous broadening of the measured optical spectra as being alloy-induced band hybridisation occurring close in energy to the CB edge. To analyze the evolution of the band gap, semi-empirical tight-binding (TB) calculations are employed to enable calculations for large supercell sizes. TB calculations reveal that the alloy CB edge is hybridized in nature, consisting at low Si and Sn compositions of an admixture of Ge L-, $\Gamma$- and X-point CB edge states, and confirm that the alloy CB edge retains primarily Ge L-point CB edge character. Our experimental measurements and theoretical calculations confirm a direct transition energy close to 1 eV in magnitude for Si and Sn compositions $x =$ 6.8 - 9.6% and $y =$ 1.6 - 2.2%.
2109.02782v3
2021-09-29
Thermal evolution of nanocrystalline co-sputtered Ni-Zr alloy films: Structural, magnetic and MD simulation studies
Monophasic and homogeneous Ni10Zr7 nanocrystalline alloy films were successfully grown at room temperature by co-sputtering in an indigenously developed three-gun DC/RF magnetron sputtering unit. The films could be produced with long-range crystallographic and chemical order in the alloy, thus overcoming the widely acknowledged inherent proclivity of the glass forming Ni-Zr couple towards amorphization. Crystallinity of these alloys is a desirable feature with regard to improved efficacy in applications such as hydrogen storage, catalytic activity and nuclear reactor engineering, to name a few. Thermal stability of this crystalline phase, being vital for transition to viable applications, was investigated through systematic annealing of the alloy films at 473 K, 673 K and 923 K for various durations. While the films were stable at 473 K, the effect of annealing at 673 K was to create segregation into nanocrystalline Ni (superparamagnetic) and amorphous Ni+Zr (non-magnetic) phases. Detailed analyses of the physical and magnetic structures before and after annealing were performed through several techniques effectual in analyzing stratified configurations and the findings were all consistent with each other. Polarized neutron and X-ray reflectometry, grazing incidence x-ray diffraction, time-of-flight secondary ion mass spectroscopy and X-ray photoelectron spectroscopy were used to gauge phase separation at nanometer length scales. SQUID based magnetometry was used to investigate macroscopic magnetic properties. Simulated annealing performed on this system using molecular dynamic calculations corroborated well with the experimental results. This study provides a thorough understanding of the creation and thermal evolution of a crystalline Ni-Zr alloy.
2109.14228v1
2022-07-06
Increasing the mobility and power-electronics figure of merit of AlGaN with atomically thin AlN/GaN digital-alloy superlattices
Alloy scattering in random AlGaN alloys drastically reduces the electron mobility and therefore the power-electronics figure of merit. As a result, Al compositions greater than 75% are required to obtain even a two-fold increase of the Baliga figure of merit compared to GaN. However, beyond approximately 80% Al composition, donors in AlGaN undergo the DX transition which makes impurity doping increasingly more difficult. Moreover, the contact resistance increases exponentially with increasing Al content, and integration with dielectrics becomes difficult due to the upward shift of the conduction band. Atomically thin superlattices of AlN and GaN, also known as digital alloys, are known to grow experimentally under appropriate growth conditions. These chemically ordered nanostructures could offer significantly enhanced figure of merit compared to their random-alloy counterparts due to the absence of alloy scattering, as well as better integration with contact metals and dielectrics. In this work, we investigate the electronic structure and phonon-limited electron mobility of atomically thin AlN/GaN digital-alloy superlattices using first-principles calculations based on density-functional and many-body perturbation theory. The band gap of the atomically thin superlattices reaches 4.8 eV, and the in-plane (out-of-plane) mobility is 369 (452) cm$^2$ V$^{-1}$ s$^{-1}$. Using the modified Baliga figure of merit that accounts for the dopant ionization energy, we demonstrate that atomically thin AlN/GaN superlattices with a monolayer sublattice periodicity have the highest modified Baliga figure of merit among several technologically relevant ultra-wide band-gap materials, including random AlGaN, $\beta$-Ga$_{2}$O$_{3}$, cBN, and diamond.
2207.02809v1
2022-08-24
In-situ neutron diffraction during reversible deuterium loading in Ti-rich and Mn-substituted Ti(Fe,Mn)0.90 alloys
Hydrogen is an efficient energy carrier that can be produced from renewable sources, enabling the transition towards CO2-free energy. Hydrogen can be stored for a long period in the solid-state, with suitable alloys. Ti-rich TiFe0.90 compound exhibits a mild activation process for the first hydrogenation, and Ti(Fe,Mn)0.90 substituted alloys can lead to the fine tuning of equilibrium pressure as a function of the final application. In this study, the crystal structure of TiFe(0.90-x)Mnx alloys (x = 0, 0.05 and 0.10) and their deuterides has been determined by in-situ neutron diffraction, while recording Pressure-Composition Isotherms at room temperature. The investigation aims at analysing the influence of Mn for Fe substitution in Ti-rich Ti(Fe,Mn)0.90 alloys on structural properties during reversible deuterium loading, which is still unsolved and seldom explored. After activation, samples have been transferred into custom-made stainless-steel and aluminium alloy cells used for in-situ neutron diffraction experiments during deuterium loading at ILL and ISIS neutron facilities, respectively. The study enables remarkable understanding on hydrogen storage, basic structural knowledge, and support to the industrial application of TiFe-type alloys for integrated hydrogen tank in energy storage systems by determining the volume expansion during deuteration. Furthermore, the study demonstrates that different contents of Mn do not significantly change the volumetric expansion during phase transitions, affecting only the deuterium content for the {\gamma} phase and the cell evolution for the \b{eta} phase. The study confirms that the deuterated structures of the {\gamma} phase upon absorption, \b{eta} and {\alpha} phase upon desorption, correspond to S.G. Cmmm, P2221 and Pm-3m, respectively.
2208.11526v2
2022-09-19
Effect of alloying on the microstructure, phase stability, hardness and partitioning behavior of a new dual-superlattice nickel-based superalloy
A novel y-y'-y" dual-superlattice superalloy, with promising mechanical properties up to elevated temperatures was recently reported. The present work employs state of the art chemical and spatial characterization techniques to study the effect systematic additions of Mo, W and Fe and variations in Nb and Al contents have on the phase fraction, thermal stability, elemental partitioning and mechanical properties. Alloys were produced through arc melting followed by heat treatment. Multi-scale characterization techniques and hardness testing were employed to characterize their microstructure, thermal stability and mechanical properties. Alterations in such properties or in elemental partitioning behaviour were then explained through thermodynamic modelling. A modest addition of 1.8 at.% Mo had a strong effect on the microstructure and thermal stability: it minimized microstructural coarsening during heat treatments while not significantly decreasing the y' solvus temperature. A reduction of Nb by 0.6 at.%, strongly reduced the y" volume fraction, without affecting the y' volume fraction. The reduced precipitate fraction led to a significant reduction in alloy hardness. Fe, added to achieve better processability and reduced material cost, decreased the y' solvus temperature and caused rapid microstructural coarsening during heat treatments, without affecting alloy hardness. A reduction of Al by 0.4 at.%, reduced the y' volume fraction and the y' solvus temperature, also without affecting alloy hardness. The addition of 0.9 at.% W decreased the y' solvus temperature but increased both precipitate volume fractions. These data will be invaluable to optimize current alloy design and to inform future alloy design efforts.
2209.08948v1
2023-11-23
3D microstructure characterization of Cu 25Cr solid state sintered alloy using X-ray computed tomography and machine learning assisted segmentation
Cu-Cr-based alloys with Cr content from 5 to 50 wt.% are widely used as electrical contacts for vacuum interrupters for medium voltage applications because of their excellent combination of mechanical, thermal, and electrical conductivity. Cu-Cr electrical contacts are usually processed by sintering or casting processes. For solid-state sintered Cu-Cr materials, the physical properties vary as a function of the Cr content, phase morphology and porosity volume fraction. Some studies have investigated the effect of the microstructural characteristics of Cu-Cr alloys with different Cr content and morphology on their properties. However, the porosity characterization and Cr spatial distribution and how they affect these alloys' physical properties are not as well documented. In this study, we report an in-depth 3D characterization of the porosity and Cr-phase of solid-state sintered Cu-25Cr alloys with three final relative densities using X-ray Computed Tomography (XCT). An image analysis algorithm assisted by a machine learning-based segmentation method has been specifically developed. Results show that for Cu-25Cr solid sintered alloys there are mainly two types of pores, pores located at the Cu/Cr interfaces, and pores within the Cu matrix. The interfacial porosity represents the larger volume fraction, over 75% of the total porosity for all cases, forming a large network of interconnected pores. With the increase of final density, the Cu-matrix becomes nearly fully dense while interfacial pores still represent the largest fraction decreases in size and volume. These interfacial pores networks are believed to be formed due to poor filling and packing of Cu around the percolated Cr-phase. These observations might be helpful to optimize the functional properties of Cu-Cr sintered alloys.
2311.13904v1
2024-02-24
Prediction of novel ordered phases in U-X (X= Zr, Sc, Ti, V, Cr, Y, Nb, Mo, Hf, Ta, W) binary alloys under high pressure
U-based binary alloys have been widely adopted in fast nuclear reactors, but their stability under extreme conditions of high-pressure is almost unknown, mounting up to latent risk in applications. Here, possible ordered phases in U-Zr system up to 200 GPa are comprehensively investigated by unbiased first-principles structure prediction. Stable U2Zr, metastable U3Zr and U4Zr phases are discovered for the first time, which exhibit strong stability under compression. They all are metallic, with 5f electrons of uranium dominating the electronic density of states near the Fermi level. Prominent ionic interactions between U and Zr atoms, as well as covalent interactions between adjacent uranium atoms, are found. The same strategy is applied to explore the stability of ordered phases in other U-based binary transition metal alloys, U-X (X= Sc, Ti, V, Cr, Y, Nb, Mo, Hf, Ta, W). Stable and metastable ordered phases similar to U-Zr alloy are unveiled, all with similar electronic structures. For these alloys, we find that the structure of U2X (X=Zr, Ti, Hf) hosts a unique hybrid phase transition similar to U2Nb, which is a superposition of a first-order transition and a second-order transition. The prediction of these novel phases not only refutes the stability of the long-believed ordered phase I4/mmm-U2Mo, but also rewrites the phase diagrams of U-X (X= Zr, Sc, Ti, V, Cr, Nb, Mo, Hf, Ta) alloys under high pressure. All of these findings promote our understanding of the high-pressure behavior of the broad category of U-based binary alloys with transition metals.
2402.15793v1
1995-11-03
Calculation of electronic properties of amorphous alloys
We describe the application of the locally-self-consistent-multiple-scattering (LSMS)[1] method to amorphous alloys. The LSMS algorithm is optimized for the Intel XP/S-150, a multiple-instruction-multiple-data parallel computer with 1024 nodes and 2 compute processors per node. The electron density at each site is determined by solving the multiple scattering equation for atoms within a specified distance of the atom under consideration. Because this method is carried out in real space it is ideal for treating amorphous alloys. We have adapted the code to the calculation of the electronic properties of amorphous alloys. In these calculations we determine the potentials in the atomic sphere approximation self consistently at each site, unlike previous calculations[2] where we determined the potentials self consistently at an average site. With these self-consistent potentials, we then calculate electronic properties of various amorphous alloy systems. We present calculated total electronic densities of states for amorphous Ni$_{80}$P$_{20}$ and Ni$_{40}$Pd$_{40}$P$_{20}$ with 300 atoms in a supercell.
9511021v1
1999-11-17
On Coherency-Induced Ordering in Substitutional Alloys: I. Analytical
As pointed out by Linus Pauling in his classic work on the relationship between crystal packing and ionic radius ratio, a difference in atomic size can be accommodated more readily by an ordered structure than by a disordered one. Because of mathematical complexity, however, very few works have been reported for substitutional alloys. In this work, coherency-induced ordering in substitutional alloys is examined through a simple model based on a two-dimensional square lattice. Within the assumption of nearest neighbor interactions on a square lattice, both modified Bragg-Williams and Onsager approaches show that coherency strain arising due to atomic mismatch can exert profound effects on order-disorder transitions in substitutional alloys. If the alloy system is elastically homogeneous and Vegard's law is obeyed, the order-disorder transition is of a second-order kinetics. If the atomic mismatches significantly deviate from Vegard's law, however, the transition may become a first-order kinetics, as the configurational free energy surface is composed of double wells. At the transition of a first-order kinetics, the lattice parameter can either increase or decrease upon heating, i.e., the lattice parameter of an ordered state can be less or greater than that of a disordered state. The results of Onsager's approach are independently confirmed with those of the Discrete Atom Method, a Monte Carlo technique predicated upon the combination of statistical mechanics and linear elasticity.
9911267v2
2000-09-05
BAs and boride III-V alloys
Boron arsenide, the typically-ignored member of the III-V arsenide series BAs-AlAs-GaAs-InAs is found to resemble silicon electronically: its Gamma conduction band minimum is p-like (Gamma_15), not s-like (Gamma_1c), it has an X_1c-like indirect band gap, and its bond charge is distributed almost equally on the two atoms in the unit cell, exhibiting nearly perfect covalency. The reasons for these are tracked down to the anomalously low atomic p orbital energy in the boron and to the unusually strong s-s repulsion in BAs relative to most other III-V compounds. We find unexpected valence band offsets of BAs with respect to GaAs and AlAs. The valence band maximum (VBM) of BAs is significantly higher than that of AlAs, despite the much smaller bond length of BAs, and the VBM of GaAs is only slightly higher than in BAs. These effects result from the unusually strong mixing of the cation and anion states at the VBM. For the BAs-GaAs alloys, we find (i) a relatively small (~3.5 eV) and composition-independent band gap bowing. This means that while addition of small amounts of nitrogen to GaAs lowers the gap, addition of small amounts of boron to GaAs raises the gap (ii) boron ``semi-localized'' states in the conduction band (similar to those in GaN-GaAs alloys), and (iii) bulk mixing enthalpies which are smaller than in GaN-GaAs alloys. The unique features of boride III-V alloys offer new opportunities in band gap engineering.
0009063v1
2002-02-17
Theoretical Study of Magnetism and Superconductivity in 3d Transition-Metal- MgB_2 Alloys
We have studied the electronic structure of 3d transition-metal- MgB_{2} alloys, Mg_{0.97}TM_{0.03}B_{2}, (TM\equiv Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) using KKR-CPA method in the atomic-sphere approximation. For unpolarized calculations, our results for Mg_{0.97}TM_{0.03}B_{2} alloys are similar to that of 3d impurities in other s and s-p metals. In particular, the local densities of states (DOS) associated with the 3d impurities are similar to our earlier work on 3d impurities in bulk Al. For spin-polarized calculations, we find only the alloys of V, Cr, Mn, Fe and Co with MgB_{2} to be magnetic of all the 3d elements. We also find that Cr and Mn in MgB_{2} have a relatively large local magnetic moment of 2.43 \mu_{B} and 2.87 \mu_{B}, respectively. We have used the unpolarized, self-consistent potentials of Mg_{0.97}TM_{0.03}B_{2} alloys, obtained within the coherent- potential approximation, to calculate the electron-phonon coupling constant \lambda using the Gaspari-Georffy formalism and the superconducting transition temperature T_{c} using the Allen-Dynes equation. We find that the calculated T_{c} is the lowest for Mg_{0.97}Cr_{0.03}B_{2} and the highest for Mg_{0.97}Zn_{0.03}B_{2}, in qualitative agreement with experiment. The calculated trend in variation of T_{c} from Mn to Zn is also similar to the available experimental data. Our analysis of the variation in T_{c}, in terms of the DOS and the spectral function along \Gamma to A direction, shows the variation to be an interplay between the total DOS at the Fermi energy and the creation/removal of states along \Gamma to A direction [P. P. Singh, cond-mat/0201093].
0202285v1
2004-03-19
Influence of intermartensitic transitions on transport properties of Ni2.16Mn0.84Ga alloy
Magnetic, transport, and x-ray diffraction measurements of ferromagnetic shape memory alloy Ni$_{2.16}$Mn$_{0.84}$Ga revealed that this alloy undergoes an intermartensitic transition upon cooling, whereas no such a transition is observed upon subsequent heating. The difference in the modulation of the martensite forming upon cooling from the high-temperature austenitic state [5-layered (5M) martensite], and the martensite forming upon the intermartensitic transition [7-layered (7M) martensite] strongly affects the magnetic and transport properties of the alloy and results in a large thermal hysteresis of the resistivity $\rho$ and magnetization $M$. The intermartensitic transition has an especially marked influence on the transport properties, as is evident from a large difference in the resistivity of the 5M and 7M martensite, $(\rho_{\mathrm{5M}} - \rho_{\mathrm{7M}})/\rho _{\mathrm{5M}} \approx 15%$, which is larger than the jump of resistivity at the martensitic transition from the cubic austenitic phase to the monoclinic 5M martensitic phase. We assume that this significant difference in $\rho$ between the martensitic phases is accounted for by nesting features of the Fermi surface. It is also suggested that the nesting hypothesis can explain the uncommon behavior of the resistivity at the martensitic transition, observed in stoichiometric and near-stoichiometric Ni-Mn-Ga alloys.
0403495v1
2005-06-17
Interface-dominated Growth of a Metastable Novel Alloy Phase
A new \textit{D0$_{23}$} metastable phase of Cu$_3$Au is found to grow at the interfaces of Au/Cu multilayers deposited by magnetron sputtering. The extent of formation of this novel alloy phase depends upon an optimal range of interfacial width primarily governed by the deposition wattage of the dc-magnetron used. Such interfacially confined growth is utilized to grow a $\sim$ 300 nm thick Au/Cu multilayer with thickness of each layer nearly equal to the optimal interfacial width which was obtained from secondary ion mass spectrometry (SIMS) data. This growth technique is observed to enhance the formation of the novel alloy phase to a considerable extent. SIMS depth profile also indicates that the mass fragment corresponding to Cu$_3$Au occupies the whole film while x-ray diffraction (XRD) shows almost all the strong peaks belonging to the \textit{D0$_{23}$} structure. High resolution cross-sectional transmission electron microscopy (HR-XTEM) shows the near perfect growth of the individual layers and also the lattice image of the alloy phase in the interfacial region. Vacuum annealing of the alloy film and XRD studies indicate stabilization of the \textit{D0$_{23}$} phase at $\sim$ 150$^{\circ}$C. The role of interfacial confinement, the interplay between interfacial strain and free energy and the hyperthermal species generated during the sputtering process are discussed.
0506427v1
2005-07-14
Superstructure in nano-crystalline Al50Cu28Fe22 alloy
This work reports the formation of nano- crystalline Al50Cu28Fe22 by high-energy milling. For obtaining the nano-crystalline material, the Al50Cu28Fe22 alloy synthesized through slow cooling of the molten alloy was subjected to ball milling, which was carried out in attritor mill at 400 rpm for 5 h, 10 h, 20 h, 40 h and 80 h with a ball to powder ratio 40 : 1 in hexane medium. The x-ray diffraction observation of ball-milled samples revealed that the milling duration of $5h$ to $40 hrs$ has led to the formation of nano-phase. The average crystallite size comprising the nano-phase has been found to be $\sim 17 nm$. When the nano-crystalline alloy, Al50Cu28Fe22 was vacuum annealed at a temperature of 500$^0C$ for 5 to 20 hrs, new structural phases representing superstructures of the parent nano-crystalline phase were found . The superstructure have been found to correspond to simple cubic with $a = \sqrt 2a_p$ and face central cubic with a = 2a_p (a_p = lattce parameter of parent nano-crystalline alloy). It has been proposed that the formation of different type of superstructure resulting due to different duration of ball milling followed by annealing is possibly governed by minimization of free energy of the disordered B2 phase.
0507343v1